Quantitative Analysis Theory

CHEM1232

2024

NAIT Coursepack 1512

School of Applied Sciences and Technology

Chemical Technology

Every effort has been made to ensure that information in this CoursePack is accurate at the time of
publication. All images are the creation of NAIT Chemical Technology unless otherwise indicated.
The Institute reserves the right to change courses if it becomes necessary so that course content
remains relevant. In such cases, the instructor will give the students clear and timely notice of the
changes.

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The Northern Alberta Institute of Technology

11762 - 106 Street, Edmonton, Alberta T5G 2R1
Table of Contents
Course Outline

1. Introduction to Analytical Chemistry 1

2. Chemical Analysis 5

3. Sampling, preparation and storage methods of analytical samples 11

4. Titrimetric Methods of Analysis 32

5. Acid / Base (Neutralization) Titrations 34

6. Electrochemistry 73

7. Complex Formation Titrations 81

8. Gravimetric Analysis 99

9. Precipitation Titrations 111

10. Determining Analytical Errors 122

11. Spectroscopy 128

Appendix

Common Indicator Colours

Ionization Constants of Aqueous Monoprotic Acids
Tolerances of Standard Laboratory Glassware and Equipment

References

NAIT Coursepack #2786 Table of Contents

1. Introduction

What is quantitative analysis / analytical chemistry

• define the subject area covered by quantitative analysis
• list and briefly explain the methods available for quantitative analysis

2. Chemical Analysis

Data Measurement
• define common terms of data measurement
• list and briefly explain the steps taken in performing a quantitative analysis
• list the factors influencing the choice of an analytical method
• list the criteria for a check sample or reference material
• understand data collected in the laboratory

Evaluation of Data
• define and calculate mean
• define precision
• calculate and use deviation from the mean, and standard deviation as absolute methods
of expressing precision
• calculate and use relative standard deviation to express precision in relative terms
• define accuracy
• differentiate between accuracy and precision
• describe calibration as a method of correcting instrumental errors
• calculate absolute error and relative error
• apply the Q test for data rejection
• identify sources of gross error
• use the appropriate number of significant figures in all calculations involving measured
quantities

3. Sampling, preparation and storage methods of analytical samples

Sampling
• define representative sampling
• define the terms used for sampling

Sampling methods, sample storage and sample planning

• list and explain sampling methods for solids, liquids and gases
• indicate the appropriate method of storage for solid, liquid and gas samples
• describe various sample planning methods

Solid sample size reduction

• list and describe methods of solid sample size reduction
• evaluate the appropriate method of size reduction based on sample type

Lab sample preparation methods

• describe the methods used for sample preparation in the laboratory
• determine where sample losses may occur during sample preparation
• identify the sources of contamination during sample preparation

NAIT Coursepack #2786 Specific Objectives i

4. Apply the principles of titrimetric methods of analysis

Terminology associated with volumetric methods

• list titrimetric methods classified in terms of end point detection method
• define titration, back-titration, primary standard, standardization, equivalence point, end
point, titration error, indicator, titrant, analyte, replicate determinations, alternation,
primary and secondary standard solutions
• perform calculations connected with the results from titrations

Terminology associated with volumetric methods

• list titrimetric methods classified in terms of end point detection method
• define titration, back-titration, primary standard, standardization, equivalence point, end
point, titration error, indicator, titrant, analyte, replicate determinations, alternation,
primary and secondary standard solutions
• perform calculations connected with the results from titrations

Reactions and reagents used in volumetric analysis

• list the characteristics of a substance suitable for use as a primary standard
• describe and explain the characteristics and preparation of primary and secondary
solutions
• list the fundamental requirements of an analysis reaction in order to carry out a
successful titrimetric analysis

5. Analyze samples using acid-base titrimetric procedures

Calculations associated with volumetric methods of analysis

• define and use the term equivalent mass in acid-base reactions
• define and use the term equivalent mass in other types of reactions
• calculate the number of equivalents given the mass and equivalent mass
• perform calculations connected with the standardization of solutions
• describe the use of titration curves in determining end point

Applications of neutralization reactions

• list and describe common titrants and primary standards used for both acids and bases

Curves for the titration of strong acids or strong bases

• calculate the pH values for key points on the titration curve of a strong acid/base titrated
with a strong base/acid
• sketch the titration curve for the titration of a strong acid/base titrated with a stro ng
base/acid
• sketch titration curves to show the effect of dilution of the titrant and/or the analyte

Acid-base indicators
• define and give examples of acid-base indicators
• choose the appropriate indicator for a strong acid-base titration
• discuss errors connected with indicator use

Dissociation equilibria for weak acids and bases

• define and evaluate the sources of pH deviation from calculated values including
temperature, activity coefficients and ionic strength

Titration curves for weak acids and bases

• write and use equilibria expressions for weak acids and bases and their conjugates
NAIT Coursepack #2786 Specific Objectives ii
 • write and interpret the expression for K w
• sketch a fractional composition diagram for a weak acid
• calculate the pH values for key points on titration curves involving a weak acid/base
titrated with a strong base/acid
• calculate the pH of a weak acid/ base solutions
• calculate the pH of a salt of a weak acid/base
• sketch titration curves for a weak acid/base titrated with a strong base/ acid
• sketch titration curves to show the effect of K a (Kb) values on the shape of the curves
• sketch titration curves to show the effect of dilution of the analyte

Buffer solutions
• define a buffer solution
• describe the preparation of a buffer of given pH and buffer capacity

Titration curves for mixtures of strong and weak acids

• sketch a titration curve for the titration of a mixture of a strong acid and a weak acid
titrated by a strong base

Polyfunctional acids and an acid salt

• sketch and label a titration curve for the titration of a polyfunctional acid titrated with a
strong base
• sketch and label a titration curve for the titration of a polyfunctional base titrated with a
strong acid
• sketch a fractional composition diagram for a polyprotic weak acid
• calculate the pH of a solution of bases
• define an acid salt as it relates to Kw, Ka and Kb
• calculate the pH values for key points on titration curves involving a polyprotic weak
acid/base titrated with a strong base/acid

6. Analyze samples using electrochemistry and redox titrations

Terminology and fundamental concepts of electrochemistry

• write half-reaction equations for REDOX reactions
• calculate the cell potential from half reactions and standard reduction potentials
• write the Nernst expression for any half reaction
• list and describe factors which influence the Nernst equation

Applications in potentiometric titration

• identify the requirements of redox titrations
• identify common oxidizing and reducing agents used for titrimetric analysis
• calculate the potential values for key points on titration curves involving redox reactions
• sketch a titration curve for a typical REDOX reaction
• differentiate between specific and general REDOX indicators
• describe the method for choosing an indicator for a REDOX reaction
• describe how REDOX indicators work
• describe how end points are detected in permanganate titrations
• describe the stability, storage and handling of permanganate solutions
• differentiate between iodimetric and iodometric titrations
• describe the preparation and properties of iodine solutions
• describe the stability of iodine solutions
• describe the use of starch as an indicator for iodimetric titrations
• define electrolysis
• describe electrodeposition and sources of error associated with electrodeposition
• calculate the amounts of products produced from electrodeposition
NAIT Coursepack #2786 Specific Objectives iii
7. Analyze samples using complexometric titrations

• define complex ion, coordination compound, ligand, coordination number, chelate,

polydentate, chelon
• define and describe the process of metal-ligand bonding
• evaluate the stability of a complex ion
• determine the coordination number of a metal ion in a ligand and relate it to its molecular
geometry
• name and write formulas of ligands
• describe valence bond theory
• define and describe crystal field theory as it relates to a ligand
• determine high and low spin octahedral configurations and ligand field strength

EDTA complexes
• sketch the structure of EDTA
• discuss the formation of metal complexes with EDTA
• write the general equation for the ionization of EDTA and for its reaction with metal ions
• sketch a titration curve for a metal-EDTA titration
• describe the effect of pH on EDTA titrations
• describe the need for other complexing agents in EDTA titrations
• describe the functioning of indicators used with EDTA
• state the functions of all reagents and procedures used in the determination of calcium
with EDTA
• list and explain the types of EDTA titrations possible
• calculate EDTA titration analysis of metals

8. Analyze samples using gravimetric procedures

• describe the historical significance of gravimetric analysis.

Properties of precipitates
• list 4 desirable characteristics of a solid that is useful for gravimetric analysis

Filterability and purity of a precipitate

• discuss factors that affect the particle size of a precipitate
• describe and use the supersaturation ratio as an indicator of particle size
• describe the mechanism of precipitate formation in terms of nucleation and crystal
growth.
• describe the experimental control of particle size
• describe the process of precipitation from homogeneous solution
• discuss various ways of obtaining products of known composition through ignition and
drying procedures

Colloidal particles
• define and give factors influencing coagulation of colloids
• describe the nature of primary adsorbed layers and counter -ion layers
• describe coprecipitation in coagulated colloids
• describe peptization of colloids
• list some practical methods for dealing with colloidal precipitates

Crystalline precipitates
• list methods of improving particle size and purity

NAIT Coursepack #2786 Specific Objectives iv

 • describe coprecipitation in terms of adsorption, occlusion, inclusion and mechanical
entrapment
• discuss digestion of crystalline precipitates
• discuss factors affecting the direction of coprecipitation errors
• list and explain briefly the effect of pH, complexation formation, diverse ions,
temperature, time, solvent and particle size on precipitate solubility

Gravimetric calculations
• determine and use appropriate gravimetric factors in calculating % of a substance in a
given sample

9. Analyze samples using precipitation titration

• sketch and discuss a precipitation titration curve

• sketch and discuss titration curves for precipitation titrations illustrating the effect of
concentration on the shape of the curve
• sketch and discuss titration curves for precipitation titrations showing the effect of K sp on
the shape of the curve
• calculate the p'analyte' values for key points on a titration curve involving a precipitation
reaction
• describe the requirements of effective indicators for precipitation titrations
• describe fractional precipitation as a method of end-point detection (Mohr)
• describe the use of an indicator blank and other methods to overcome indicator error
• describe complex formation as a method of end-point detection (Volhard)
• describe the action of adsorption indicators in precipitation reactions (Fajan)
• state the functions of all reagents and procedures used in the standardization of silver
nitrate and the determination of chloride by the Volhard method
• state the function of all reagents and procedures used in the standardization of silver
nitrate and the determination of chloride by the Fajans method

10. Determining Analytical Errors

• calculate the error for analytical results

11. Analyze inorganic samples using visible light

• explain the difference between emission and absorption methods

• define Beers - Lambert law and do calculations using it
• define and describe deviations from Beers – Lambert Law
• be able to use the two methods for quantitating experimental results
• describe and draw simple spectroscopic instrumentation

NAIT Coursepack #2786 Specific Objectives v

1. Introduction to Analytical Chemistry

Objectives of Quantitative Chemistry

(Gilreath, Elementary Quantitative Chemistry, W. H. Freeman and Company, 1969, p 3)

The laboratory procedures in quantitative chemistry are of disciplinal, educational, and practical
value to a student.

Disciplinal Values. In the analysis of a substance a student strives to obtain results that are close
to percentages that are known only to the instructor. In seeking a high degree of accura cy certain
personal qualities are essential;
1) The student must have a sense of objective honesty in the evaluation of laboratory
measurements.
2) He must be able to follow directions carefully and intelligently, and to make accurate
observations and readings.
3) He must acquire neat and precise working habits, and always record laboratory data
following a systematic form in a suitable notebook.

Educational Values. Of the students who complete a course in quantitative chemistry, very few will
ever enter a profession that requires routine analytical determinations. However, the educational
values within the study are fully as important as any other values which may be attributed to the
course. Among the educational advantages are the following:
1) The student is given an opportunity to use certain aspects of applied mathematics.
2) He supplements and expands his knowledge of some basic principles of analytical
chemistry.
3) He becomes familiar with the literature of analytical chemistry.

Practical Values. In most chemistry curriculums, quantitative chemistry is the first course in which
the attainment of precise and accurate results is a primary objective.
1) to attain accurate results a student must acquire manipulative ability and reasonable speed
in the handling of chemical equipment.
2) He must appreciate the limitations of the methods and equipment he uses, and the
magnitude of possible errors that may be involved.
3) He must be able to make rapid calculations from analytical observations to a precision
warranted by the data included.

Finally, a course in quantitative chemistry will provide the student with confidence in his laboratory
skills. This confidence facilitates the determination of the proper approach to almost any type of
laboratory problem; this it is essential in advanced courses, in research and in the problems that
may be faced in professional and industrial laboratories.

NAIT Coursepack #2786 Introduction to Analytical Chemistry 1

What Is Analytical Chemistry?
The branch of chemistry that deals with separation identification, and determination of constitvents in a
sample.
- includes equilibrium.

Chemistry
Biochemistry
Inorganic Chemistry
Organic Chemistry
Biology Physical Chemistry
Botany Physics
Genetics Astrophysics
Microbiology Astronomy
Molecular Biology Biophysics
Zoology

Geology Engineering
Geophysics Civil
Geochemistry Chemical
Paleontology Electrical
Paleobiology Mechanical

Analytical
Chemistry

Environmental Medicine
Sciences Clinical Chemistry
Ecology Medicinal Chemistry
Meteorology Pharmacy
Oceanography Toxicology

Agriculture
Agronomy
Materials Science
Animal Science
Metallurgy
Crop Science
Polymers
Food Science
Solid State
Horticulture
Soil Science Social Sciences
Archeology
Anthropology
Forensics

Skoog, West, Holler and Crouch, Analytical Chemistry, An Introduction, Saunders College Publishing, 7 th Edition, 2000, p. 4

NAIT Coursepack #2786 Introduction to Analytical Chemistry 2

Quantitative analysis:

how much of a component is in the sample

steal: Fe, Mn, Co, Cu, Ni, C

mineral components - to determine type of steel * have units

Qualitative analysis:
What is a sample composed of

steal: Fe, Mn, Co, Cu, Ni, C ex; carbon steal contain carbon

*don't have units

Sample Size Constituent Types

Type of
Type of Analysis Sample Size Analyte Level
Constituent
Macro >0.1 g Major 1% - 100%
Semimicro 0.01 – 0.1 g Minor 0.01% (100 ppm) - 1%
Micro 0.0001 – 0.01 Trace 1 ppb – 100 ppm
g
Ultramicro <10-4 g Ultratrace <1 ppb
NAIT2014

• Gravimetry:
mass --> Cu, SO4 -2
precipitation
• Titrimetry:
solution based - have to have a way to show when the reaction is complete
- indicator, potential, conductivity
• Electrochemical:
apply voltage to precipitate an analyte coulometry

• Spectral methods:
the behavior of electromagnetic radiation (CMR)

• Chromatography:

how a substance interacts with a mobile phase vs. stationary phase

• Chemometrics:
statistics of analysis

NAIT Coursepack #2786 Introduction to Analytical Chemistry 3

 Method Approx. Approx. Selectivity Speed Cost Principal
Range, M Precision, % Uses
Gravimetry 10-1 – 10-2 0.1 Poor - Slow Low Inorg
moderate
Titrimetry 10-1 – 10-4 0.1 -1.0 Poor - Moderate Low Inorg, org
moderate
Potentiometry 10-1 – 10-6 2.0 Good Fast Low Inorg
Electrogravimetry 10-1 – 10-4 0.01 – 2.0 Moderate Slow – Moderate Inorg, org
Coulometry moderate
Voltametry 10-3 – 10-10 2.0 – 5.0 Good Moderate Moderate Inorg, org
Spectrophotometry 10-3 – 10-6 2.0 Good - Fast - Low – Inorg, org
moderate moderate moderate
Fluorometry 10-6 – 10-9 2.0 – 5.0 Moderate Moderate Moderate Org
Atomic 10-3 – 10-9 2.0 – 10.0 Good Fast Moderate Inorg,
Spectroscopy – high multielement
Chromatography 10-3 – 10-9 2.0 – 5.0 Good Fast - Moderate Org,
moderate – high multicompon
ent
Kinetic Methods 10-2 – 10-10 2.0 – 10.0 Good - Fast - Moderate Inorg, org,
moderate moderate enzymes
NAIT2014

NAIT Coursepack #2786 Introduction to Analytical Chemistry 4

2. Chemical Analysis
Data measurement

Fundamentally, quantitative analysis requires that all possible care is taken to guard against loss of
material or the introduction of foreign substances. Attention to detail and the assurance that the
operating conditions do not destroy or diminish the confidence in the analysis. The confidence of
the analytical results are based on the magnitude and uncertainty of the measurements.
Identifying the limitations of the results strengthens the analysis.

Data collected in the laboratory

1. recognize sources of analytical limitations.

Does the equipment/glassware impact the confidence of the result?
► What is the difference between a graduated cylinder and a volumetric pipette? Why
and when one or the other is used.
► When is the top loading balance (2 decimals) used versus when is the analytical
balance used (4 decimals)? Is the balance verified as being in calibration? Is the
verification recorded? Is it clean, level and in working condition?

2. recognize where the analyte could be lost or gained.

The key is to ensure that the equipment/glassware and lab area are always kept clean
and organized.
► This can be physical. Is the analyte left on the glassware or equipment? Could it be
transferred or carried away on stirring rods or stir bars? How can this be avoided?
► This can be chemical. What are the properties of the analyte? Sodium is everywhere,
so if the analyte is sodium how can contamination be overcome? Would there be a
significant impact on the result? Is the analyte highly active? Will it react with reagents
or contaminants?

3. recognize whether results are acceptable or unacceptable during the analysis.

A close agreement of results should be expected but does not indicate the accuracy of
results.
► To avoid loss of valuable working time and the possibility of having to repeat the
analysis, know how to determine whether collected data is "good" or acceptable.
Replicates of pipetted analyte should display consistently similar results. Using masses
of samples, the difference in mass must be taken into account when comparing data.
► Know what is being analyzed and the units that represent the quantitation of the
analyte. If there is a check or quality control standard ensure the data produced is
within ~2.5% of the actual value. (Note: this is an arbitrary number based on
experience – a suitable statistical evaluation of the method/sample/process should be
conducted). Is there a control chart that could indicate deviation from an expected
value?
► Is a calibration curve being produced? Is the representation linear (R 2 = 1)? Does the
sample fall within the analytical range?

4. know when an analysis is complete versus when another sample should be conducted.
Only the analyst can decide if the results are worthy of full c onfidence.
► Never dispose of any standards or samples before checking the data.
► The analyst is the only one who knows the full history of the analysis.

NAIT Coursepack #2786 Chemical Analysis 1

5. record the proper data
All data is important! It needs to be written clearly in ink and in a logbook!
► Read and record measured values obtained from scales as accurately as possible; this
means read value to one more digit than there are scale divisions. A buret has 0.1 mL
scale divisions so read/record volumes to two decimals.
► The result is the last digit in a measured value is estimated and so has some
uncertainty (error) associated with it, but this estimated digit is still thought to convey
useful information and so is considered a significant digit.
► All digits in a measured value except the last digit are considered to be certain, do not
have error.
► For a digital read-out, the last digit is considered to be uncertain; this can be seen when
the last digit “flickers” between two values.
► Recorded values must be written absolutely clearly!! Take time and effort to form the
digits properly.

Common terms:

Species chemical of interest Fe 3+ vs Fe 2+

Analyte
is a chemical or substance constituent that is of interest

Contaminants
impurities introduced into the sample or sample preparation process that may ulter after the accuracy and
precision of results

Sample contamination can occur at any step in the sampling and sample preparation process.
Blank samples are used to detect the source of contaminants that may alter the precision or
accuracy of test values from actual field samples. Blank samples are used to analyze
contaminants that may be introduced from the field, reagents, instrumentation, and transport to
and from the laboratory.

Interferent a species other than the analyte increases or decreases the analytical result more
or less than what is actually present

Masking transformation of an interfering species into a form that cannot be detected

Matrix or sample matrix everything in the sample that is not the analyte,
cu (s) --> HNO3 + H2O => Cu2+
into
solution matrix
Replicates portion of same material carried out through procedure at same time, same way.
Measurement uncertainties cause replicates to vary. Assesses the variability and
guard against gross error of a single sample analysis

Specific refers to technique/reaction which responds to one analyte, selective refers to a

Cu 2+ technique/reaction that responds to a few analytes.

Validity are the results correct

NAIT Coursepack #2786 Chemical Analysis 2

Error:
the difference between a measured value and the true value or the estimated uncertainty in the
measurement or experiment

All chemical analysis will involve errors and uncertainties.

The objective is to minimize errors and determine their size based on the maximum error that
can be tolerated in the result.

Errors arise from a variety of sources: sampling, sample preparation, instruments, standards,
analysts, environment, random variations and others.

Method selection and analysis time have the greatest impacts on the acceptable maximum
error.

Gross error: (blunders)

- spill
- contaminants
- incorrect measurement
- adding the incorrect amount of analyte or reagent
- using the wrong reagent

NAIT Coursepack #2786 Chemical Analysis 3

Method Selection Method-based on sample.
apparatus based in sensitivity accuracy, time, money
available

Is it homogeneous / heterogeneous, -sample

size from sample protocol

decrease particle size, mix, consider losses

[water?]

Prep lab sample-do replicates,

convert sample to measureable
form:

- dissolve
- convert to appropriate species ex;
Mn 2+ to MnO4 -
- control or eliminate interferences
- consider specific and selectivity of the
method
- add masking agents or adjust pH

Calibrate and measure get a value

concentration = constant x measurement

Compute analyte concentration

use statistics to determine reliability

Feedback systems such as quality control

mechanisms help assure results.

Skoog, West, Holler and Crouch, Analytical Chemistry, An Introduction, Saunders College Publishing, 7 th Edition, 2000, p. 6

NAIT Coursepack #2786 Chemical Analysis 4

 Final choice- Selecting a method requires carefully assessing the analysis requirements. Usually,
the most important aspect is accuracy so the analysis will produce the most accurate result.
- type of analysis being followed
-> environment, health or safety labs are dictated by compliance requirnment

how close thePrecision- extent in which agreement is achieved for a series of standards. This can be
results are repeatability (analysis by an analyst on a piece of equipment over a short time span),
intermediate precision (compares method results over a number of weeks), and reproducibility
(precision obtained between different laboratories). These reflect variations in operators,
standards, reagents, equipment, and consumables.

Sensitivity- response of a method (or instrument) to the concentration of the analyte or property.
Can be thought of as the slope of an analytical calibration gr aph.

Specificity- ability of the method to respond to a single analyte. Typically there is response to
other components.

Selectivity- ability of the method to distinguish the analyte from other species. If the analyte
reacts with a reagent to form a colored species are other colored species also present?

Robustness and Ruggedness– is a measure of an analytical procedure to remain unaffected by

small, but deliberate changes in method parameters. Such conditions can be temperature,
extraction or shaking time, shaking technique, pH, purity of reagents, moisture content of
sample, sample size, etc. This can provide an indication of the procedure’s reliability during
normal use.

Robustness the ability to reproduce the method/results in different laboratories

Ruggedness though of reproductivity

Scale of Operation- the amount of sample available for the analysis, the expected concentration
of analyte in the samples, and the minimum amount of analyte to produce an analytical signal

Analytical range- refers to the concentrations within the solutions that will be me asured by the
method rather than the concentration in the original sample. The graphical presentation of this
response function is usually called a calibration or standard curve.
The analytical range is generally considered to begin at the limit of quantitation (LOQ) but is not
a requirement. It is desirable that the analytical range during method validation be wider than
that recommended for the routine application of the method.
The upper level of the analytical range may be determined by limitations of the instrument itself.
The desired calibration plot is usually a linear model but if the response is nonlinear a response
function can be determined and used as part of the analytical range. The response function or
factor should be limited to a quadratic rather than higher polynomial functions. Logarithmic,
exponential and power functions may also be used for nonlinear models.

http://www.labcompliance.com/tutorial/methods/default.aspx#03_standard

ideally: - non destructive

- want a dynamic range - selective
- flexible - cheap/fast
- accuracy

NAIT Coursepack #2786 Chemical Analysis 5

 significant figures represent precision of the value
- an indicator of how it was measured (or calculated)
Evaluation of data

Reporting analytical data / results

 usually require calculations, so combining values which contain uncertain digits.
 do not round values during a calculation; carry at least 1 insignificant digit (probably 2 or 3)
through calculation and round the final value.
 use the odd/even rule to round the “exactly half” uncertain (insignificant) digit.
 Rules: for x and , retain the minimum significant digits.
for + and –, retain minimum decimals.
for a log value, the number of significant digits = number of decimals

Mean or average

Precision

- the closeness with which the results of replicate analysis of a sample agree
- dispersion or scattering around the mean
-in terms of standard deviation

Precision can be measure through the use of replicate control and test samples. Deviation in
the precision of analysis can be due to sampling error and sample preparation inconsistencies
in the laboratory.

Standard Deviation
a measure of reproducibility of the results. Replicates with identical results would have a
standard deviation of zero. A large standardization indicates the results are not very
reproducible.

Relative Standard Deviation

- a standardized measure of dispersion of probability distribution or frequency distribution -> also known as the
coefficient of variation (CV)

%RSD
a calculated value that indicates the reproducibility of results. = std dev/ mean x 100

a %RSD of 1% or less would indicate the results are reproducible

Accuracy
the "trueness" or the closeness of the analytical results to the 'true' value.

Accuracy is the blend of errors (random and systematic) that cannot be directly measured. For
lowest # statistical validity most test results are reported as a mean of several measurements.
replicates is 3

NAIT Coursepack #2786 Chemical Analysis 6

 The difference between accuracy and precision
Accuracy: how close an analytical value is to the true value
Precision: how close together measurement values are to one another

Absolute error

amount of physical error in a measurement

- the uncertainty which is expressed using the relevant units 32.5 g _+ 0.1 g

Relative error

uncertainty of measurement (combination of known equipment's glass ware + balance instrument) compare to the size
of measurement

30.12 mL x 1.3 % / 100 % = 0.3916 mL

30.12 mL _+ 0.3916 mL

NAIT Coursepack #2786 Chemical Analysis 7

3. Sampling, preparation and storage methods of analytical samples
Sampling and analysis are closely related and dependent on each other. Sampling is the process
of taking a small portion of a larger quantity. The sample should represent the composition of the
whole material.

Representative Samples

1. Collection and Preparation of the Representative Sample

• sampling takes place outside the laboratory.
• several operations (steps) can be required that can lead to a large amount of sampling
error.
• inaccuracies of a representative sample can include:

- sampling bias
- contamination
- procedure error - incorrect for the situation and/or incorrect sampling frequency
- analytical method may limit the types of samples obtained

2. Cost
expensive - important to get the best results with a minimum number of samples
- minimized cost by preparation

3. Purpose of Sampling
- estimation of the value of large lots
- determine purity
- process control
- determination of reaction rate
- process mass balance - getting out what is putting in

4. Legal Implications
• rigid documentation and procedures are used to ensure the integrity of the sample and
sample data LMS

NAIT Coursepack #2786 Sampling and Sample Preparation 8

5. Documentation and QC Samples
Used to ensure the integrity of samples which need to be legally defensible

- sample labelling
- field logbooks
- sample chain custody
- field blanks
- rinse blanks

who takes the sampling record + labels

sample contains

time stamp Representive contamination

Sample

location weather cleaning

storage

Sampling terminology

1. Bulk or Lot
Large mass that must be sampled
- original location, river, lakes, snow pile...
original material

2. Increment
Mass of sample recovered in one single operation

- portion of mass from the bulk/Lot

- not necessarily representative
- individual sample

NAIT Coursepack #2786 Sampling and Sample Preparation 9

 3. Grab Sample
- specific cases only
- sample collected all at once at one point
- representative of a specific location at a point
- preformed method for hazardous sample, cause minimize contact time

4. Representative Sample
a small portion of a lot ( large population, bulk of material) that
contains the same concentration as the lot

5. Subsample
portion of sample

6. Laboratory Sample
- subsample prepared for chemical analysis
- primary material delivered to the lab

7. Test Specimen
part of lab sample taken for measurement
- replicate measurement

high sampling error

test specimen

test specimen

W. H w z, “ ”, Pure & Appl. Chem., V . 62, . 6, .1193-1208, 1990

(U R 1990)

NAIT Coursepack #2786 Sampling and Sample Preparation 10

Sampling Methods for Solids, Gases and Liquids

Gases / Air / Vapours Samples

• very few homogeneity issues arise with gases in storage vessels
Gas and vapour samples depend on the environment at which they exist (STP)
Precautions must be taken to clear taps, connecting lines and valves
• Air is a unique matrix with potentially extreme variations and heterogeneity

Sampling equipment and preservation of gas samples

- stainless steel consider or tedlar teflon bags are commonly used
- contamination is avoided by purging the containers
- traps with solid sorbent
- volatile gasses or filteration

Preservation: pumps are used to sample a specific volume

little need for preservation or preparation
if collected properly - the sample is stable

Liquid/Water Samples
• Liquids are typically homogeneous but depend on the environment in which they exist.
Care must be taken when separate phases exist (relative volumes of each phase must be
known but each phase is separately sampled)
• Water and groundwater samples may have typical seasonal variations depending on the
water balance due to recent precipitation and water usage
• Surface waters of various types can be very heterogeneous both based in location and time
of sampling as a result of flow and stratification, making it difficult to collect representative
samples

beverages, natural waters, solvents, process solutions, bodily fluids, etc

Sampling equipment and preservation of liquid samples

- composition change can result from chemical, physical or biological processes
- wide month (plastic) containers (jars) or glass bottles
- Fill the container completely to minimize air contact because air contains many things and can
react with the thing in the container

Preservation:

pH and temperature control

limit exposure to light or the atmosphere
may add preservatives

NAIT Coursepack #2786 Sampling and Sample Preparation 11

 Solid Samples
• The representativeness depends largely on the types of sample matrices
• Usually heterogeneous and so exceeds the errors introduced during sample collection and
analysis
Sample preparation process (subsampling, mixing, grinding, and sieving) is very important
for representative samples
ores, soils, sediments, pellets. capsules, tablets, feed, sheet materials, biological specimins

Sampling equipment and preservation of solid samples

- composition change is likely to occur due to volatile components, biodegradation or
chemical reactivity (commonly redox)

grab sampler, corers, scoops, shovels, soil punches, augers, sample thief!
sampling plan must be in place to ensure a representative sample

Preservation:

- temperature control, prevent biodegradation or loss volatile species

- completely fill the container, no loss of volatile species
- dry or ash and blend or grind
- stored in sealed jars or bags

NAIT Coursepack #2786 Sampling and Sample Preparation 12

Sample Planning
Where and when to collect samples

Two main categories:

1. Judgmental Sampling
- Non-statistically based approach
- Involve selection of sampling units on the basis of expert knowledge or professional
judgment
• Selection of sampling units (i.e. the number, locations, and/or timing of collecting samples)
is based on knowledge of the prior information on the sampling site, visual inspection (e.g.
leaks, discoloration) and/or personal knowledge and experience

. preferred when schedule and budget are tight (emergency response)

. preferred at the early early stage of site investigation
. preferred when screening for the presence or absence of contamination - lead to
whether or not statistical sampling follow-up is needed.

-> does not support any statistical interpretation of the sampling results

2. Probability-based Sampling
• Applies sampling theory and involves random selection of sampling units
• When this approach is used, inferences can be drawn about the sample population

Simple Random Sampling

– Particular sampling units (i.e. locations and/or times) are selected randomly
– Each sampling point is selected independently from all other points
– Is the simplest and the most fundamental probability-based sampling approach
– This approach assumes that variability of a sampled medium is insignificant
– It is appropriate for relatively uniform or homogenous populations such as vessels,
lagoon, etc.
– Can be applied for sites with little background information

Advantages:

. statistically unbased estimates of the mean

. easy to implement and understand
. straightforward sample size calculations and data analysis

NAIT Coursepack #2786 Sampling and Sample Preparation 13

 Stratified Random Sampling
– Divides sampling population into several non-overlapping (mutually exclusive) strata
and within each stratum a simple random sampling is employed
– Each stratum is relatively more homogenous
– Strata may be chosen on the basis of spatial or temporal proximity of the units, or on
the basis of pre-existing information or professional judgment about the site
– Strata could be “temporal” or “spatial”
• Temporal strata permits different samples to be selected for specified time periods,
i.e. day vs. evening, weekdays vs. weekends, four
season of the year, etc.
• Spatial strata are more common and come with many
varieties: it can be based on sampling depth (stratified
lakes, soil, or sediment cores), ages, land types,
zones of contamination, wind direction (downwind vs.
upwind, etc.)

Advantages:

. ability to adjust the sample size depending on cost of sampling and other variations
. provides greater precision and cost savings

Systematic Random and Grid Sampling

samples are taken at regularly spaced intervals over space and time (equal distance intervals
along a line or a grid pattern)

– Systematic grids can be square,

rectangular, triangular, or radial
– The systematic grid sampling subdivides
the area of interest by using grids and
then collects samples from the nodes
(intersection of the grid line) or a fixed
location (e.g. center) of each grid. An
initial location or time is chosen at
random, and then the remaining
sampling locations are defined so that all
locations are at regular intervals over an
area (grid) or time (systematic)
– In random systematic sampling, the area
of interest is subdivided into grids and
then samples are collected within each
grid using random sampling approach
– Calculations are straightforward

NAIT Coursepack #2786 Sampling and Sample Preparation 14

 Composite Sampling
– Volumes of material from several of the selected
sampling units are physically combined and mixed
in an effort to form a single homogeneous sample,
which is then analyzed
– Can be very cost effective, when analysis costs
are large compared to sampling costs) because it
reduces the number of chemical analyses needed
- requires that there are no safety hazards or potential biases (losses of volatile components)
are associated with the process
- often used in conjunction with other sample approaches

Adaptive Cluster Sampling

– If samples are taken using simple random
sampling, and additional samples are
taken at locations where measurements
exceed some threshold value
– Good application of this approach when
have to outline the contamination borders
– Initial measurements are made using
random sampling approach (bold squares
in the figure), when a sampling unit is
found to show a characteristic of interest
(i.e. contaminant concentration of concern, ecological effect as indicated by the shaded
areas in the figure), additional sampling units adjacent to the original unit are selected, and
measurements are made
useful for estimating or searching for rare characteristics in a population and is appropriate for
inexpensive, rapid measurement

Solid Sample Size Reduction

Definitions:
– Homogeneity
an even distribution of analyte throughout the sample most solid samples are not homogeneous
and must be reduced in size

– Size reduction

a unit operation where parties are reduced in size by pressure of mechanical force

NAIT Coursepack #2786 Sampling and Sample Preparation 15

Size reduction equipment:

– Two categories:
1. Industrial
a) Course feed (30-90 cm)
–Jaw crusher
–Gyrator or cone crusher
–Hammer mill
b) Intermediate feed (5-30 cm)
–Crushing rolls
–Gravity stamp mill
c) Fine feed
–Ball and rod mill

2. Laboratory
jaw crusher
- crushing rolls
-pulverate
-hammer mill
-mortars

Laboratory Size Reduction: starts with under 5cm diameter

– Jaw Crusher

intermediate size reduction

– Crushing Rolls

•Consists of two heavy cylinders revolving towards each

other
•Considerable amount of wear on rollers
•Diameter and spacing may be varied

intermediate size reduction

NAIT Coursepack #2786 Sampling and Sample Preparation 16

– Pulverizer
•Two circular discs moving
against each other
•Particle size is limited by the gap
between the fixed disk and
moving disk
fine side reduction

– Hammer Mill
•Heavy blocks of steel attached by pins to disk revolving at high
speed
•Hammers deliver heavy blows to feed material while in
suspension driving it against breaker plate until fine enough to
pass through the openings at the bottom
can be use for fine pulverizing

– Mortar and Pestle units

– Tyler Screen Analysis or Sieve Screening/Analysis

• Many natural (ores, soils, etc.) and manufactured materials
occur in a dispersive form
– Consist of differently shaped and sized particles
• The particle size distribution is responsible for important
physical and chemical properties
– Mechanical bulk behaviour, surface reaction, miscibility,
filtration properties, conductivity, etc.
• It’s important to know the particle distribution, particularly with
the context of quality assurance in the production of bulk
goods
– If particle distribution changes during the manufacturing
process, then the quality of the finished product will also
change
– Only continuous monitoring of the particle size distribution can guarantee a constant
product quality
• The oldest and the best known method is particle size determination by sieve analysis

NAIT Coursepack #2786 Sampling and Sample Preparation 17

 • Sieve analysis or Screening

. particle size distribution

. mechanical method
. screen shaker - agitates the sample to sake smaller particles down wards

• Used for choosing the proper choice of representative subsampling

– After doing all statistical calculations we can identify the optimal size of particles
– After the size reduction steps, we are more interested in getting the largest fraction of
the particle size of interest

Tyler Screens
- screen number represent the number of opening per linear inch

-the bigger the number the smaller the opening

Mass reduction:

– solid samples often require preparation before analysis – unlike most gases and liquids
– reducing the sample’s average particle size may need to be reduced to allow for a smaller,
more manageable representative sample
– most analytical methods require the analyte to be in solution
– can be done both in the primary (sampling on the site), secondary (subsequent sample
reduction done in the lab)

Mass reduction methods:

1. Grab sampling
– obtaining the sample by simply scooping the top of
the lot
– This method is the most often used method in
practice (eg. Van Veen Grab)
– reflects information only at the point in time that the
sample was collected, and then only if the sample
was properly collected

by for the worst performer

- should be avoided

NAIT Coursepack #2786 Sampling and Sample Preparation 18

2. Alternate shoveling

- the mass is reduced by shoveling the material into 2 piles in an alternating fashion
- one pile is randomly chosen and subsequently into a new small piles and continues until the desired sample
size is reduced

3. Fractional shoveling
- the same method as alternative shoveling but 3 or more piles (instead of 2)
* shoveling methods have the most unreliable , biased results

4. A sectorial splitter

a rotating metal one with ridges and valleys

– The receiving vessels depend on the size and design

of the splitter.
– Small splitters may use a test tube while large splitters
may require beakers or jars.
top

5. Paper cone sectorial splitter

– uses a sheet of paper folded to resemble the ridges and
valleys of a sectorial splitter fluted filter
– It is inexpensive and the materials needed are commonly
available.
– On the other hand, it is more prone to operator error than
mechanical sectorial splitters.
– Paper cones take a few minutes to make, but have the
advantage of being disposable.

NAIT Coursepack #2786 Sampling and Sample Preparation 19

6. Riffle splitters
– come in a wide variety, some more correct
than others
– they are operated pouring the material
over a number of chutes, every other
leading to two different recipient reservoirs
– the number and width of chutes vary
between models

intermediate performance
. suitable for routine, non critical worry
- reliable and representative samples
-the longer the number of chuts, the smaller the bias
- closed riffles splitters provide better results than open models

7. Rotary riffle splitters or Rotational splitters

– basically consist of a rotating nozzle pouring the sample over a number of radial chutes
– in some models the chutes width is variable
– rotational splitters are dynamically equivalent to riffle splitters

-one of the best method

. sample is divided in a perfectly random manner
. require little maintenance
. quick processes

8. Incremental sampling
– An increment is a group of particles or material physically extracted from the lot (or sample)
with a single operation of the sampling device.
– The sample (or subsample) is made from the reunion of many increments (N = 30
increments is recommended) taken at random locations across the lot (or sample) to be
represented.

incremental sampling increases the probability of sampling each

location of the lof.
If preformed with the correct sampling device can provide a suitable
sub sample

NAIT Coursepack #2786 Sampling and Sample Preparation 20

9. Coning and Quartering
– involves mixing and then pouring the sample into the
shape of a cone.
– The cone is flattened, divided into four sections with a
cross cutter having 90°angles, or by first cutting it in
half with a stiff piece of material (e.g., a sheet of
plastic or paper), and then dividing each half to get
quarters.
– Alternate quarters (splits) are combined to make a
subsample, and one subsample is chosen at random
for any additional mass reduction until the desired
subsample mass is reached.

10. Rolling and Quartering

– is variation on coning and quartering.
– The sample is placed in a conical pile on a large sheet of material with a smooth surface,
such as: glazed paper, a thin plastic sheet, or rubberized cloth. The cone is then flattened
and the material is mixed by rolling it back and forth.
– The material is returned to the centre by lifting all four corners of the sheet, flattened out,
and then split in half using the quartering procedure.

11. Table Sampler

– consists of an inclined surface with various triangular prisms placed to divide the sample
– the surface is vibrated and the particles move from the top to the bottom
– Like the riffle splitter, this device splits the sample in one pass.
– However, the number of increments associated with this technique is small with a tendency
to allow large grouping and segregation errors to remain.
– The device is also bulky and not readily available.

12. Boernerdivider
– consists of central cone over which the sample is poured, dividing it across 38 radially
distributed chutes
– Every second chute also leads to one of two accumulating reservoirs
– designed for grains

provides the marginally most accurate and precise overall mass reduction with a very narrow replicate
distribution

not a good method

13. “Spoon method”
– a method is used in official seed testing.
– The lot material is spread in an “S” like pattern layer by layer into a flat container.
– Afterwards, five sub-samples are started by inserting a sharp spatula and extracting all the
way to the bottom by a small square scoop
– The five sub-samples are combined to yield the final composite sample

When choosing a specific method for mass reduction, either in the field or in the laboratory,
reliability and representativity (accuracy and reproducibility) of final sub-samples is the primary
focus

NAIT Coursepack #2786 Sampling and Sample Preparation 21

Laboratory sample preparation methods

Solid Sample Dissolution

1. Decomposition of Solid Samples

Most analyses require that the sample be rendered soluble for chemical analysis. Mild solvents
should always be tried first. Whenever possible, water is the solvent of choice. If the
substance is insoluble in water, dilute solutions of acids and bases a nd certain organic solvents
are tried. Only if these methods are unsuccessful are strong acids or other harsher solvents
tried. In general, polar and ionic substances dissolve more readily in water or polar organic
solvent such as methanol and acetonitrile while nonpolar substances dissolve in solvents such
as dichloromethane and ether.

in general: rule of solubility "like dissolves like"

- some solids are particularty diificult to break down.

siliceovy minerals can only be analyzed after the sillicare structure is destroyed. --> done using treatment
with select reagents.

2. Liquid reagents

after water...mineral acids (HCl, HNO3, H2SO4)

Solutions of bases (NaOH + KOH) occasionally used

NAIT Coursepack #2786 Sampling and Sample Preparation 22

3. Acid Treatment

Acids may be classified as nonoxidizing acids such as hydrochloric, sulfuric, and dilute
perchloric and oxidizing acids such as nitric and hot concentrate of perchloric acid. In general,
any metal above hydrogen in the activity series of metals will displace the hydrogen ion from an
acid solution and thus be dissolved, although some of the reactions are slow. Metals below
hydrogen in the electromotive series generally require use of an oxidizing agent fo r dissolution.
An acid solution may not only serve as an acid but also as a complexing or a precipitating
agent. Chloride ion, for example, can form soluble complexes with many metal ions thus
increasing the solubility of salts of these metal ions.

The use of strong acid to dissolve samples introduces the possibility of loss by volatilization of
one or more components of the sample particularly if a hot medium is employed. Volatile weak
acids may be lost and many other substances, which are nominally nonvolatile, may b e lost to
an extent significant in highly accurate work.

HCl: (activity series) dissovlves most coomon elements except Sb, Bi, As, Cu, Hg, Ag

HNO3: Hot acid will dissolve all common metals with the exception of Al and Cr. The
protective coating of the Al and Cr oxides (that forms in due process) inhibits their further
dissolution. Sn, W and Sb form slightly soluble salts. Their separation from the rest of
sample is accomplished by filtration. Use HNO 3 only when HCl will not dissolve the metal in
question.

H2SO4: Dilute sulfuric acid dissolves all common metals except lead, antimony, bismuth,
arsenic, copper, mercury and silver. Hot sulfuric acid is an efficient solvent due to its high
boiling point (340º C). Many substances will dissolve at elevated temperatures. Organic
substances are oxidized by hot H 2SO4. Thus, this acid is used to eliminate the organic part
of the sample. An anion of a less volatile acid may be displaced from solution by boiling
and evaporation with sulfuric acid. (e.g. NO 3-)

HClO4: Hot concentrated perchloric acid dissolves all common metals. It is a strong
oxidizing agent and should be used with extreme caution since easily oxidizable
substances including some organic substances react with explosive violence. It will attack
a number of Fe alloys and stainless steels. Cold or diluted HClO 4 is not dangerous. The
concentrated acid is 60-72 % strong.

HF: The prime use for this acid is in decomposing silica rocks providing Si is not the
analyte. HF forms the volatile SiF 4 and the residue is then treated with H 2SO4 or HClO4 to
remove the excess of HF. Further treatment of the residue could be necessary because
some substances form stable fluoride complexes. At times, HF is used for the dissolution of
steels. It is worth noting that this acid is very corrosive to skin and it should be handled with
extreme care.

NAIT Coursepack #2786 Sampling and Sample Preparation 23

4. Oxidizing Reagents

Aqua Regia: This reagent (3 parts HCl + 1 part HNO 3) attacks all metals. This
combination provides hydrochloric acid in an oxidizing medium. The complexing
characteristic of the chloride ion is particularly significant in the dissolution of gold or
platinum.

Br2 or H2O2: Addition of Br 2 or H2O2 to mineral acid will increase their oxidizing power,
hence improved solvent action.

5. Fusions

many mineral (oxides) and alloys (mixtures of metals) can be dissolved by acids.

In general, the sample is mixed with the flux (the mass of flux about 10 or more times larger
than the mass of sample) in a metallic crucible (Fe, Ni or Pt). The mixture is subjected to high
temperatures (300-1000º C). The outcome is the conversion of insoluble compounds into
water- soluble Na or K salts.

Fluxes that will attack acidic compounds are: carbonates, hydroxides, borates and peroxides.

Fluxes that will attack basic compounds are: persulfates, acid fluorides and boric oxide.

The use of fluxes is normally avoided. The disadvantages are: the large amount of reagents
required, having to handle crucibles at high temperatures, the formation of volatile compounds,
the resulting large solution volumes, and the possible contamination of samples. Therefore, it
is recommended to dissolve most of the sample in acids, and treat the residue with the flux,
minimizing the above disadvantages.

NAIT Coursepack #2786 Sampling and Sample Preparation 24

 b. Flux reagents:

Na2CO3: Used to decompose silicates and some other minerals. Heating to 1200º C
(Pt crucible) will result in conversion of metallic constituents into acid soluble
carbonates or oxides.

Al2(SiO3)3 + 4 Na2CO3 → 3 Na2SiO3 + 2 NaAlO2 + 4 CO2

K2S2O7: Potassium pyrosulfate is a strong acid flux used to treat metallic oxides. Fusion
is performed at 400 o C in porcelain crucibles or vitreous glass beakers. The reagent
breaks down according to the following reactions:

K2S2O7 → K2SO4 + SO3

Fe2O3 + 3 SO3 → Fe2(SO4)3

c. Miscellaneous fluxes:

boric oxide, CaCO3 + NH4Cl mixture - popular for decomposition of silicates.

6. Decomposition of Organic Compounds

The elemental analysis of an organic compound requires its oxidation into CO 2 and H2O. At
times, addition of a reducing compound is required to break the covalent bond and set the
element free.

The oxidation procedures are grouped into two categories:

i) wet ashing: use HCIO4 or H2SO4

ii) dry ashing: ignitionina stream of O2

NAIT Coursepack #2786 Sampling and Sample Preparation 25

Sample losses during preparation

Dust or Particulates
At a minimum, all ash or finely ground samples should be covered before they are moved

Volatilization
Moisture, organics and some elements (As, Sb, Sn, Po, Pb, Se, Ge, B) are prone to
volatilization
Special precautions during sample preparation are necessary to avoid volatilization or to
capture volatilized material

Interactions with containers

Adsorption can occur between some samples and glass and plastic containers.
Hydrating container surfaces can minimize losses due to adsorption
High temperatures can increase possibility of chemical reaction
Scratches or abrasions can increase surface area where sample loss is more likely
Discard containers where the inner surface is scratched or abraded.

Sources of Contamination
- very important to implement and maintain measures to eliminate contamination errors resulting
from sampling

Sample environment - direct exposure to air-borne contaminants and environmental changes

humidity, temp and exposure to light

- contamination can happen anywhere including ovens, muffle furnaces, fridges, freezers, etc

Sample container - store in a compatible inert container

- minimize the time between sample collection for analysis
- leaching from container
- loss of analyte through surface adsorption

Sampling Tools - unclean sampling tools can lead to contamination

- use separate dedicated tools for specific analytes/analysis
- use clean glassware

Contamination from other laboratory samples - cross – contamination is contamination from other
samples in the lab.
- Via damaged or cracked containers
-close proximity to other samples.
- untidy work benches or weighing balance tools
- uncleaned glassware

NAIT Coursepack #2786 Sampling and Sample Preparation 26

Contamination from substandard reagents – reagents that do not have the required purity

- use reliable vendors/manufacturers

- use proper handling technique

Contamination from analyst - can be a major contributor to contamination

- follow required standards of hygiene including using disposable

- head covers, face mask, clean lab clothing, removal jewelry, etc.

Contamination arising from lab traffic - Visitors in the laboratory

may require restriction on street clothing for foot wear that could introduce outside dust

NAIT Coursepack #2786 Sampling and Sample Preparation 27

4. Titrimetric Methods of Analysis
…based on endpoint detection method

Indicator – represented by a colour change. The indicator usually an acid -base or redox.
Potentiometer – measures electrical potential. Redox titrations.
pH meter – ion selective electrode – measures H+
Conductivity – measures ions in solution. Not selective, measures all ions. Note not all ions
behave the same in solution so the measurement is dependent on ion mobility and ionic
strength.
Colour change – often redox reactions will change colour due to change in oxidation state – no
added indicator is required.
Precipitation – formation of a precipitate. Often a back titration or special indicator is required.
Isothermal titration calorimeter – measures heat produced or consumed by a biochemical reaction
Thermometric – measures rate of the temperature change of a reaction
Spectroscopy – measures light absorption and related to Beer's Law
Amperometry – measures current – redox reactions

Requirements of analytical titrations

1) reaction must be known
2) reaction must be fast and irreversible
3) reaction must be specific
4- thermal must be a measurement, indication of the completion of the reaction

Review of terms

Titration: involves determination of the volume of standard required to react completely with the
analyte contained in a known mass or volume of a sample.

Back-titration: when an excess of the standard solution is added and then the excess is
determined by titration with a second standard reagent.

Equivalence point: the point at which the standard solution added is chemically equivalent to
the substance with which it reacts.

Endpoint: point at which some physical change associated with the equivalence point occurs.

Titration error: the difference in volume between the endpoint and the equivalence point.

Indicator: a substance that undergoes a change in colour as a result of the concentration

changes that occur in the vicinity of the equivalence point.

Titrant: a reagent solution of known concentration.

NAIT Coursepack #2786 Titrimetric Methods of Analysis 28

 Replicate determinations:

doing one ore more determination of the same using the same method sample

Alternations: consists of carrying out a series of laboratory operations on standards and

samples in an alternating sequence so that errors resulting from changes in operator
techniques, solution concentration, instrument drift, endpoint judgment, and so forth tend to
be cancelled.

Blank determination: a titration where all the conditions are virtually identical with those
employed in the analysis except no analyte is added which is used to obtain corrections to
be applied to the measurement of the unknowns.

Standardization: process by which the concentration of a solution is determined by titration

using a known amount of analyte.

Primary standard: a highly pure substance required for establishing the concentration of a
standard solution.
requirements - highly pure – needs to be handled to ensure purity. Greater than 99.98%
pure.
stable – at minimum should be stable over 120C this allows for effective
drying
- should not change under normal laboratory conditions or during
storage. ie atmospheric absorption of water, O 2 or CO2
soluble – must be soluble in solvent
has high molar mass
able to weigh out without special precautions or handling
produce negligible titration error
chemical reaction must be fast and stoichiometric with the titrant

Standard solution preparation:

1. directly by dissolving a carefully weighed quantity of highly pure compound and diluting
to exactly a known volume. - solution - aliquot
2. indirectly by titrating a solution containing a weighed quantity of a pure compound with a
standard solution solid

Secondary standard: a substance that can be used for standardization but has been analyzed
for the analyte using a primary standard.

Titration Calculation

1.354 g sample of sodium nitrate contaminated with NaCl was dissolved in small amount of water
and filled to the mark in the 100 mL volumetric flask. To titrate chlorides in 10.00 mL sample
35.70 mL of 0.01021 M AgNO 3 was used. What is the percent purity of the sample?

AgNO3(aq) + NaCl(aq) → NaNO3(aq) + AgCl(aq)

35.70 mL AgNO3 x 0.01021 mol AgNO 3 x 1 mol NaCl x 0.1 L x 58.44 g NaCl = 0.2130 g
1 L AgNO3 1 mol AgNO3 10.00 mL 1 mol NaCl
original - impurity
1.354 g – 0.2103 g x 100 = 84.27% pure
1.354 g
10.00 mL

sample (1.354 g)
NAIT Coursepack #2786 Titrimetric Methods of Analysis 100 mL VF titrated with 29
0.01021M AgNO3
36.70 mL
 4. Acid / Base (Neutralization) Titrations
Properties of strong acids and strong bases:

completely ionize or dissociate when placed in water (molecular form of substance does not exist
in solution – no reactant remains)
• are strong electrolytes
• have a large Ka and Kb

Ionization is a process where a molecular compound reacts with water to form ions (process
common to acids)

Examples of strong acids:

HCl(aq) HClO4(aq)
HBr(aq) HClO3(aq)
HI(aq) H2SO4(aq) (only the first proton HSO 4- is weak)
HNO3(aq)

Dissociation is a process in which ionic compounds form ions in an aqueous solution (process
common to strong bases)

Examples of strong bases:

LiOH CsOH
NaOH Ca(OH) 2 (not very soluble)
KOH Sr(OH) 2 (not very soluble)
RbOH Ba(OH) 2 (not very soluble)

Titration reaction for a strong acid with a strong base

Acid Base salt water
HA + MOH → MA + H2O
A = anion
M = metal ion

Example titration reaction:

HCl + NaOH → NaCl + H2O

Titration Calculations:

A 30.00 mL sample of H2SO4 was titrated using 18.25 mL of 1.30 M sodium hydroxide. Determine
the concentration of the sulfuric acid.

H2SO4 + 2NaOH --> Na2SO4 + 2H2O

=0.395 mol/L H2SO4

18.25 mL NaOH x 1.30 mol NaOH / 1 L x 1mol H2SO4 / 2mol NaOH x 1/30.00 mL H2SO4

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 30

 Normality – A Review

equivalent s of solute
N =
litre of solution

- one equivalent of any acid is equal to the mass of acid in grams capable of supplying 1
mol of hydrogen ions
- one equivalent of any base is equal to the mass of base in grams that will combine with 1
mol hydrogen ions or supply 1 mol hydroxide ions

HCl / NaOH: 1M=1N

H2SO4/ Ca(OH) 2: 1M=2N
H3PO4/Al(OH) 3: 1M=3N

- one equivalent of acid will combine with one equivalent of base. The equivalent mass (g)
of an acid is determined by dividing the formula mass of the acid by the number of moles of
hydrogen ions
- the equivalent mass (g) of a base is determined by dividing the formula mass of the base
by the number of moles of hydroxide ions supplied by the base

HCl: 36.46 g/1 eq NaOH: 40.00 g/1 eq

H2SO4: 98.08 g/2 eq Ca(OH) 2: 74.09 g/2 eq
H3PO4: 98.00 g/3 eq Al(OH) 3: 78.00 g/3 eq

Calculate the normality of an aqueous phosphoric acid solution containing 185 g of H 3PO4 in
0.75 L of solution in reactions that replace all three hydrogen ions.

185g H3PO4 / 0.75L x 1 mol H3PO4 / 98.00g x 3 eq/1mol = 7.55 eq/L H3PO4

Calculate the number of grams of H 2SO4 necessary to prepare 520.0 mL of 0.100 N aqueous
sulfuric acid solution in reactions that replace both hydrogen ions.

( 0.5200L H2SO4 ) x ( 0.100 eq H2SO4 / 1 L) x (1 mol/2eq) x (98.08g/ 1 mol H2SO4) = 2.55g H2SO4

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 31

Theoretical Titration Curve:

pH versus the titrant volume (mL NaOH).

• the titration curve is a chart showing how the pH changes in the titrate solution
(Erlenmeyer) as the titration reaction proceeds from initial concentration of analyte to well
past the equivalence, i.e. over-titrated

• the titration graph is pH of titrate solution versus the volume of titrant added, in mL

• the various regions of the titration curve are:

o initial concentration of analyte at 0 mL titrant added.
o pre-equivalence (under-titrated portion), the first gradual pH change portion – the pH is
affected by the concentration of the analyte in the titrate.
o equivalence point region, the vertical line portion.
o post-equivalence (over-titrated region), the second gradual pH change portion – the pH
is affected by the concentration of the excess titrant being added to the titrate.

Titration of 20.0mL 0.100 M HCl with 0.100M NaOH

14.0
post equivalence point base
12.0
10.0
8.0 endpoint/ equivalence point
pH

6.0 salt & water

4.0 strong electrolyte

2.0 Initial
pre equivalence point
0.0 acid only
0.000 10.000 20.000 30.000 40.000 50.000
Volume of 0.100M NaOH Added
NAIT2014

Unique Property of a Strong Acid / Strong Base Titration Reaction:

• the products of a strong acid and a strong base are water and an ionic salt.

• pure water self-ionizes to produce equal amounts of H 1+ and OH1– resulting in a pH of 7.00.

• the ionic salt product from strong acid/strong base reactions do not react with water to
produce any H1+ or OH1–, so the pH is unaffected by the ionic salt product.

• therefore, the pH at the equivalence point for a strong acid/strong base titration is pH = 7.00

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 32

Titration reaction for a strong base with a strong acid

NaOH(aq) + HCl(aq) → NaCl(aq) + H2O

The same steps in the calculation of pH will be followed as with the titration of the acid.

Titration of 20.0mL 0.100 M NaOH with 0.100 M HCl

14.000
base pre-endpoint
12.000
10.000
8.000 equivalence point
pH

6.000
pH = 7
4.000
post equivalence point
2.000
0.000 acid
0.000 10.000 20.000 30.000 40.000 50.000
Volume of 0.100 M HCl Added, mL
NAIT2014

Effects of reducing titrant and titrate concentrations

Concept:
Decreasing the titrant and titrand will change the pH of the titrate solution as indicated below:

Titration curve:

Effects of Reducing HCl and NaOH Concentrations

14.000

12.000

10.000
always going to be 7
8.000 0.1 M HCl with 0.1 M NaOH
pH

6.000 0.01 M HCl with 0.01 M NaOH

4.000 0.001 M HCl with 0.001 M NaOH

2.000

0.000
0.000 5.000 10.000 15.000 20.000 25.000 30.000 35.000 40.000
Volume of NaOH Added, mL
NAIT2014

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 33

Observations:
• as the concentration of the strong acid analyte and the strong base titrant decrease, the
titration curve begins higher up and ends lower down; the equivalence point remains in the
same place.
• the result of lower analyte concentration is the length of the vertical equivalence point line
becomes shorter, which represents a smaller change in pH at the equivalence point.
• when the length of the vertical equivalence point line is less than 2 pH units long, then the
size of the pH change at the equivalence point is less than 100 and the indicator reaction
would fail, hence the titration analysis would fail.
• for strong acid analysis, 0.0010 M acid is about the lower limit in concentration that can be
successfully analyzed for.
• for the reverse analysis, i.e. analyzing for a strong base with a strong acid titrant, the same
limit would hold for the same reasons, the graphs would all just be upside –down.

Applications of Neutralization Titration Reactions

Common acid titrants:

HCl (most common), H2SO4 , HClO4

Advantages of these acid titrants:

• dilute solutions are stable indefinitely, no change in concentration.

• these titrants will not cause precipitation of most cations.

Primary standards use to standardize acid titrants:

1. Na2CO3
not the best choice
molar mass 105.99 is low which can increase weighing error
requires heating (180°C) to decompose any NaHCO 3
hygroscopic, therefore weighing by difference is essential
requires boiling prior to the equivalence point to decompose H 2CO3 and remove CO2.

2. TRIS/THAM (tris-(hydroxymethyl)aminomethane
the better choice
molar mass of 121.1
requires no special drying, weighing or reaction procedures.

Common base titrants:

NaOH (most common), KOH, Ba(OH) 2

Disadvantages with these base titrants:

base solutions rapidly absorb atmospheric carbon dioxide to produce carbonate
carbonate contamination decreases the sharpness of the end point
carbonate in the titrant will result in a negative systematic error in a titration when a basic
indicator is used (e.g. phenolphthalein). The CO 32- only reacts with one hydronium ion at
this point forming HCO 31-. This makes the base titrant have an effective concentration
that is less than stated and thus introduces a carbonate error
basic titrants should be stored in polyethylene bottles to avoid reaction of the base with the
glass. Sodium hydroxide can react with the glass to form sodium silicates.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 34

Methods of reducing carbonate in basic titrants:
boil the water used to prepare the basic titrant solution. This is needed to remove carbon
dioxide from the water which can react with the base to form carbonate and water
OH1- + CO2 → CO32- + H2O

cool the solution during the addition of the base to avoid excessive heating which can promote
the reaction of the base with carbon dioxide in the air
prepare concentrated stock solutions of base since sodium carbonate has a low solubility in
strong base solutions (e.g. 50% NaOH). The solid sodium carbonate which settles may
be avoided from contaminating the basic solution by decanting the liquid or filtering the
solid sodium carbonate

Primary standards used to standardize base titrants:

Potassium hydrogen phthalate, “KHP”

• molar mass of 204.23 is high reducing weighing errors
• requires no special drying, weighing and reaction procedures.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 35

Calculation of a Theoretical Titration Curve

A theoretical titration curve is calculated from a substance in the titrate with known concentration
and a titrant with a known concentration so the points along the curve can be calculated and
graphed.

Calculation example:
titratnt titrant
HCl + NaOH --> NaCl + H2O
50.00 mL of 0.100 M HCl titrated with 0.100 M NaOH

i. Calculation of the equivalence point volume:

(50.00 mL HCl) x ( 0.1 mol HCl /1L) x (1 mol NaOH / 1 mol HCl) x ( 1L / 0.100 mol NaOH) = 50.00mL NaOH

ii. Initial pH Calculation; no base added:

Concept:
The Ka is used to calculate the [H 1+] in the titrate since only the acid is in solution.

Calculation:
HCl is a strong acid and has a very large Ka.

HCl + H2O → H3O1+ + Cl1–

pH= -log [H+]

= -log(0.100)
= 1.00

iii. Partially Titrated pH Calculation:

Concept:
The titrate concentration (acid) will be reduced as the titrant substance (base) immediately
reacts with the titrate (acid).

Calculation steps:
• calculate the total mol acid present in titrate before titrant added
• calculate the mol of acid that reacted due to the addition of titrant
• calculate the mol of acid remaining after the addition of titrant
• calculate the concentration (M) of acid in the titrate after the addition of titrant. The
volume of titrant added must be added to the original titrate volume to calculate the new
titrate volume
• determine the [H1+] in the titrate formed from the acid and calculate pH.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 36

 Ex: Calculate the pH after 1.00 mL of 0.100 M NaOH is added to the 50.00 mL of 0.100
M HCl

[H+] = (mol HCl initial - mol HCl reacted) / volume HCl initial + volume NaOH reacted

(0.100 mol H+ / L x 0.0500L) - (0.100 mol NaOH/ L x 0.001L NaOH x 1molH+ / 1mol NaOH)

0.0500L + 0.001L

=0.0961 mol/L H+ pH= -log (0.0961) = 1.017

iv. pH at the Equivalence Point:

species in solution
: Concept:
-> can continue the
At the equivalence point only the salt will be present in the titrate solution. The pH at the
same calculation equivalence point will be the pH of the salt.
to just before
(not including) the The salt formed from a strong acid and strong base is a neutral salt.
equivarnce point volume
Ionization of water:
_ volume of titrant HOH(l) + HOH(l) → H3O1+(aq) + OH1-(aq)
increases - concentration
of titrant (analyte) Salt:
decreases NaCl(aq) → Na1+(aq) + Cl1-(aq)
_ total volume increases
Substances in titrate:
pH:

Kw = 1 x 10 ^-14 = [H3O+] [OH-]

[H3O+] = square root of (1 x 10^-14
= 1 x 10^-7 M
pH = -log (1x10^-7)

v. pH After the Equivalence Point:

Concept:
The titrant added will increase the [OH 1-] since sodium hydroxide will not react with the salt.

Calculation steps:
• determine the volume of excess NaOH (titrant) added after the equivalence point
• determine the quantity (mmol) of excess NaOH added
• determine the total volume of the titrate
• calculate the concentration of NaOH in the titrate and then the [OH 1-]
• calculate pOH
• calculate pH; pH = pKw – pOH

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 37

Ex: Calculate the pH after 51.00 mL of NaOH are added.

[OH-] = (0.100 m/L NaOH) (1.00mL NaOH) / 50.00mL acid + 51.00mL base = 9.901x 10^-4 mol/L OH-

pOH = -log(9.901 x 10^-4)

= 3.004
pH= 14 - 3.004 = 10.996

Titration of 50.0mL 0.100 M HCl with 0.100M NaOH

14.0
12.0
10.0
8.0
pH

6.0
4.0
2.0
0.0
0.000 10.000 20.000 30.000 40.000 50.000 60.000 70.000
Volume of 0.100M NaOH Added
NAIT2014

Calculate the pH at: 15 mL, 35 mL, 55 mL and 65 ml and plot on the graph.

(49 mL) x (0.1 mol / L) ( 50.00 mL) - ( 0.1 mol / L OH -) x ( 49.00 mL) x ( 1 mol H+ / 1 mol OH-)

50 + 49

= 1.0101 x 10 ^ -3 M H+

pH = 2.996

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 38

Indicators for Acid Base Titrations

Requirements of an acid base indicator

the indicator must respond to changes in pH and for this reason must also have a weak acid/weak
base structure

Acid – type indicator:

HIn + H2O H3O1+ + In1-

(weak acid) (weak base)

Base – type indicator:

In + H2O InH1+ + OH1-

The indicator must have an intense color change so that only a few drops of indicator are needed
to respond to pH change. The quantity of indicator must be small so that it does not affect the
equivalence point for the analyte

The change in the color of the indicator is due to structural change differences between the acid
and base forms of the indicator

structures that confine electrons will shift the wavelengths of light that are absorbed to the uv end
of the spectrum (see acid form of phenolphthalein - colorless)

structures that free electrons such as alternating double and single bonds (conjugation) and any
region of the molecule that is flat will free electrons to extend over the molecule causing the
wavelengths of light that are absorbed to shift to a longer wavelength (e.g. blue-green). This will
result in the light that passes through the solution to appear reddish in color (see base form of
phenolphthalein – reddish)

Phenolphthalein in acid and base forms

HIn + H2O H3O1+ + In1-

(weak acid) (weak base)

pKa = pKPhenInd 8.4 start seeing pink

HO

O OH
OH

+ HOH H3O1+
-
O
O
O

Colorless reddish-pink

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 39

The human eye can see color change with only about a 100 fold change in the concentration of the
base/acid structures of the indicator. Thus for phenolphthalein:

[In1 − ] 10
High pH = pka + log = 9.4 + log = 10.4 bright pink
[HIn] 1

[In1 − ] 1
Low pH = pka + log = 9.4 + log = 8.4 start seeing pink
[HIn] 0.1

Factors to consider in choosing an indicator

titration process must produce a minimum of 2 pH units of change at the equivalence point, i.e. the
vertical line portion of the titration curve must be a minimum of 2 pH units long, so the pH change
is fast enough to produce a very fast change in the indicator equilibrium which produces a very fast
(“sharp”) colour change. What factors affect this degree of change?

choose an indicator compound so that the indicator pK a is approximately the same as the pH of the
equivalence point.

choose the indicator compound so that the end point colour is on the vertical line portion of the
titration curve. This will ensure that the colour change will be “sharp” or fast, occurring with the
addition of only 1-2 drops of titrant

precision = sharp end point (i.e. ± ½ drop)

accuracy = end point position (i.e. small titration error)

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 40

Ranking the choice of indicator

First; the best situation is if the end point is on the vertical line portion of the titration curve and
exactly equal to the equivalence point; this would have a sharp end point colour change and
have no titration error: end point volume = equivalence point vo lume.

Second; the next best has the end point on the vertical line portion of the titration curve and
after the equivalence point; this would have a sharp end point colour change and have a
positive titration (determinant/systematic) error: end point volume > equivalence point
volume. The titration error might be corrected by:

a blank titration
perform standardization and analysis exactly the same way.

Third; an “ok” situation has the end point on the vertical line portion of the titration curve and
before the equivalence point: this would have a sharp end point colour change and have a
negative titration (determinent/systematic) error: end point volume < equ ivalence point
volume. This titration error cannot be corrected with a blank but might be corrected by
performing the standardization and the analysis exactly the same way.

Fourth; the worst situation which is a useless situation (titration would fail) is the end point falls
either before or after the vertical line portion of the titration curve; the end point is not actually
on the vertical line portion. The end point colour change would be very slow (not “sharp” or
fast) so very difficult to determine the actual end point colour change and the titration errors
would be extremely large.

Rank these two indicators for this titration of a weak acid with a strong base.
Indicator pkeq pH range Rank
Thymolphthalein 9.9 9.3 colourless 10.5 blue 2
Naphtholphthalein 8.0 7.3 pale red 8.7 green-blue 3
Phenolphthalein 9.4 8.4 colourless 10.4 pink 1
Phenol red 7.2 6.4 yellow 8.0 4

NAIT2017

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 41

Weak Acid/Weak Base Chemistries

Analysis Reaction
• weak acids can be titrated with a strong base because the presence of the strong base forces
the acid/base reaction to completion, the reaction is irreversible:

CH3CO2H + NaOH → CH3CO21– + Na1+ + H2O

WB
• weak bases can be titrated with a strong acid because the presence of the strong acid forces
the acid/base reaction to completion, the reaction is irreversible:

CH3NH2 + HCl → CH3NH31+ + Cl1–

• these acid/base reactions are also fast, have a known and constant reacting ratio and there is
a large pH change at the equivalence point to trigger the indicator for a successful end point.

The Weak Acid Titration Curve

• the weak acid analyte titration curve begins at a higher pH because a weak acid solution has
a higher initial pH, fewer acid hydrogens at a given concentration.
• the partially titrated portion of a weak acid titration curve has both the weak acid and its
conjugate base present so this section is a buffer solution.
• there is a vertical equivalence point line with the equivalence point located above pH of 7.0
because the solution of the conjugate base has a basic pH, where the specific pH depends
on the concentration of the conjugate base.
• the over-titrated portion of the titration curve is the same as it was for the strong acid titration
curves because it is the same titrant, NaOH.

The Weak Base Titration Curve

• the weak base analyte titration curve begins at a lower pH because a weak base solution has
a lower initial pH, fewer hydroxide ions at a given concentration
• the partially titrated portion of a weak base titration curve has both the weak base and its
conjugate acid present so this section is a buffer solution.
• there is a vertical equivalence point line with the equivalence point located below pH of 7.0
because the solution of the conjugate acid has an acidic pH, where the spe cific pH depends
on the concentration of the conjugate base.
• the over-titrated portion of the titration curve is the same as it was for the strong base titration
curves because it is the same titrant, HCl.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 42

Sources of pH deviation from the calculated

Temperature effects on Kw and Ka

The ion product constant for water, Kw, and the ionization constants for acids, K a, are affected
by temperature. For example the equilibrium for water is influenced by temperature.

HOH + HOH H3O1+ + OH1-

The effect of temperature on the K w for water

T (°C) Kw pKw neutral pH neutral pOH

-14
0 0.114 × 10 14.94 7.47 7.47

10 0.293 × 10 -14 14.53 7.27 7.27

20 0.681 × 10 -14 14.17 7.08 7.08

30 1.471 × 10 -14 13.83 6.92 6.92

40 2.916 × 10 -14 13.54 6.77 6.77

-14
50 5.476 × 10 13.26 6.63 6.63

60 9.550 × 10 -14 13.02 6.51 6.51

-14
70 15.85 × 10 12.80 6.40 6.40

80 25.12 × 10 -14 12.60 6.30 6.30

-14
90 38.02 × 10 12.42 6.21 6.21

100 51.3 × 10 -14 12.29 6.14 6.14

NAIT2014
The table clearly indicates that an increase in temperature shifts the equilibrium to the right
increasing the [H3O1+] and thus reducing pH.

Similarly the Ka for acids will also increase causing more product to form and thus increasing the
[H3O1+] and reducing pH. The effects of temperature on the K a values for glycolic acid and lactic
acid are shown in the table below. Once again higher temperatures increas e the product
concentrations for the equilibrium reducing pH.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 43

The effect of temperature on K a

Glycolic acid
Temperature ( oC) Ka pH of 1.0 M solution
0 1.334 x 10 -4 1.94
25 1.475 x 10 -4 1.92

Lactic acid
Temperature ( oC) Ka pH of 1.0 M solution
25 1.374 x 10 -4 1.93
100 8.4 x 10-4 1.54
www.rejuvilab.com/ph.pdf

Activity coefficients and relationship between “activity” and molar concentrations of

species in solution

The purpose of activity coefficients, , is to relate the molar concentration of a species, [X], in
solution to its activity, ax .

ax =  x [X]

As an example the real definition of pH is:

pH = -log aH1+ = -log[H1+]H1+

A pH meter is actually measuring the hydrogen ion activity, not its concentration.

Ionic species are the principal components in solution that show deviations between molar
concentration and activity. Low ionic strengths show minimal effects and have an activity near
unity and thus have little influence on the equilibrium compared to mo lar concentration. As the
ionic strength increases the effect of neighbouring ions reduces the influence of a given ion on the
chemical equilibrium and thus the “activity” of the ion is less than its molar concentration. This is
due to a smaller activity coefficient, .

Neutral molecules are considered to have an activity of 1.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 44

Ionic strength, µ, used in the calculation of the activity coefficient is influenced by:
the number of different ions in solution
the molar concentration of each of the ions
the charge on the ion.

The equation for ionic strength reflects these factors:

1
 = (c1 Z12 + c2 Z22 + c3 Z32 + ...........
2
where c is the molar concentration of the various ions (1,2,3, etc.) and Z is the charge on the
various ions

Factors affecting the activity coefficient, , for ionic species are the following:

increase in ionic strength as ionic strength increases, activity coefficient decreases

Why?

1
v
ffi ,

±1
±3
,

Magnitude of the ionic charge

Why?
the greater the charge of the iron, the more rapidly magnitude is absolute, therefore _+ 3
has a greater magnitude than _+ 1 (+3 has a very similar magnitude -3)

as charge increases the departure of its activity coefficient from the unity increases

as magnitude increases activity must be corrected

Effect of the diameter of the hydrated ion (effective diameter)

Why?
the smaller the hydrated diameter of the iron the more important activity effects become

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 45

 quiz pg 30-41

Fractional Composition of Monoprotic Weak acids

A fractional composition displays the species in solution. The diagram indicates what species are
predominant at given points during the titration reaction.
Alpha is fraction of each species at a given pH. All species exist together in equilibrium and the pH
determines the fraction of each.

Acetic Acid: Ka(HAc) = 1.8 x 10 -5 pKa = 4.74

Plot area = rectangle
Y = fraction, range = 0 – 1
X = pH, range = 0 – 14
Cross-over occurs at 4.74 at  = 0.5
memorize Draw an ‘x’ through the center (pKa) extending 1 pH unit to either side
Extend the tails 1 more pH unit to either side
The drawing doesn’t have to be perfect, the information is still there.

Do: Ammonium hydroxide: k b = 1.8 x 10-5

All NH4OH all NH 4+

NH4 +
predom
NH4OH
predominants

no NH4OH
No NH4 +

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 46

Calculation of a Theoretical Weak Acid Titration Curve

As with SA/SB the titration curve is S shaped and the [H+] will be affected by:

- the Ka of the weak acid before the equivalnce point

- remember Ka = [ H+] [A-] / [HA]

pKa = pH + log [ Salt] \ [Acid]

- Kb of the salt of the weak acid us used to find the pH at eq point

• titrate 50.00 mL of 0.100 M acetic acid with 0.200 M NaOH titrant:

Titration reaction: CH3CO2H + NaOH → CH3CO21– + Na1+ + H2O

Equivalence Point Volume

• the equivalence point is when mol NaOH = mol HOAc

(50.00 ml HOAc) x (0.100mol HOAc / L ) x (1 mol NaOH/ 1 mol HOAc ) x (1 L / 0.2 mol NaOH)

= 25 mL NaOH

Initial pH of the Analyte

• acetic acid is a weak acid, use WA Ka to determine pH
• an approximation using the formula [H +] = √(Ka x Cwa); where Cwa is the concentration of the
weak acid. This is usually good if the C wa is >(1000 x Ka) or Cwa > 1000
Ka

HOAc + H2O H3O1+ + OAc1–

0.1 / 1.75 x 10 ^ -6
H+ = square root (1.75 x 10 ^ -5) (0.1) = 5714 > 1000

= 1.32 x 10 ^ -5 M no ice table required

pH = -log (1.32 x 10 ^ -5 M ) = 2.88

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 47

Addition of 5.00 mL of 0.200 M NaOH
• some of the acetic acid is neutralized and some acetate ion is produced.
• the combination of some acetic acid and some acetate ion forms a buffer.
• this pH calculation is a buffer calculation by partial neutralization.
HOAc + NaOH (limiting reagent) → OAc1– + Na1+ + H2O
mL x MHA start – mL x Mbase x mol ratio mL x Mbase x mol ratio
[HA]remaining=( ) and [A-]formed =
Total Volume Total volume

([ H+ ] x [A - ] formed)
pH is then found from the Ka expression: Ka = [ HA ]remaining
or using the[H+] = ka[HA]
[A-]
[ A-]
Henderson-Hasselbalch equation: pH = pKa + log ([ HA] formed )
remaining

HOAc + H2O H3O1+ + OAc1– (Ka = 1.75 x 10 -5)

Addition of 12.50 mL NaOH: ½ Titration

• at 12.50 mL, ½ of the acetic acid is neutralized, converted to acetate, and ½ of the acetic acid
remains.
• this means the concentration of acetic acid = concentration of acetate and the ratio of the
concentrations = 1, hence, pH = pKa

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 48

Addition of 25.00 mL NaOH:
• all of the acetic acid is neutralized; no acetic acid remains.
• the titrate solution at the equivalence point contains only the acetate ion.
• the acetate ion is the conjugate base so the pH of this solution will be basic because acetate
is a weak base.
• [A-] is determined and pOH is found from the Kb expression of the conjugate base.
• Recall Ka*Kb = Kw and A- + H2O HA + OH-
• you must first calculate the concentration of the acetate ion.
mL x Mbase x mol ratio
[A–] =
Total Volume
Then; using [A-]: [OH-] = √(Kb x [A- ])
Finally, determine pH

Addition of 26.00 mL of NaOH: Over-Titration

• after the equivalence point, the extra NaOH has nothing to react with so NaOH in excess of
25.0 mL just adds a strong base to the titrate solution as OH 1– ions.
• the pH after the end point is caused by the concentration of the unreacted NaOH in solution.
• [OH1–] = concentration of excess OH 1– in the titrate.

Addition of 30.00 mL of NaOH: Over-Titration

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 49

Summary of pH at various mL of NaOH

mL 0.0 5.00 12.50 25.00 26.00 30.00

pH

Titration Curve for 50.0 mL 0.100M Acetic Acid Titrated with 0.200M NaOH
16

14

12

10
pH

0
0 5 10 15 20 25 30 35
Volume NaOH added, mL

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 50

 lower [WA] : lower [A-]
lower [A-] = more acidic
Change in the Titration Curve as Analyte Concentration Decreases lower pH
WA
• as the concentration of the acetic acid decreases, the initial pH of the titrate solution
increases because it is less acidic.
• regardless of the acetic acid concentration, the pH at ½ titrated will remain the same because
pH = pKa is not a function of acetic acid or acetate concentration but rather the ratio of the
concentrations which is 1.00 at ½ way.
• the pH of the equivalence point will change as the acetic acid concentration decreases,
becoming less basic because there is less of the basic acetate ion in solution; less base,
then less basic, then lower pH.
• as the analyte concentration is decreased, the concentration of the titrant, NaOH, is also
decrease so the titration volume remains large.
• as the NaOH concentration is decreased, the pH in the over-titrated portion will be lower
because the solution will be less basic.
• over-all, the length of the vertical equivalence point line will become shorter as the analyte
concentration decreases, and when the length of this vertical line is less than 2 pH units long,
the indicator action will fail and so the analysis will fail.

Summary: pH Values for Decreasing CH3COOH / NaOH Concentration, Constant K a

Conc., M Conc., M initial pH ½ way pH eq pt pH 30 mL pH

CH3COOH NaOH 0 mL 10mL 20 mL
0.1 0.2 2.88 4.76 8.73 12.52
0.01 0.02 3.38 4.76 8.23 11.52
0.001 0.002 3.88 4.76 7.73 10.52

Titration Curve for Different Concentrations of Acetic Acid Titrated with NaOH
16

14

12

10
pH

0
0 5 10 15 20 25 30 35
Volume NaOH added, mL

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 51

Change in the Titration Curve as Strength of Weak Acid Decreases

• the value of the Ka decreases done at constant concentration of the weak acids, i.e. 0.10 M
acid.
• as the analyte becomes a weaker acid (K a decreases), the initial pH will become higher
because the weak acid solution are less acidic because the acids are weaker, producing less
hydrogen ions, so begin at a higher pH.
• the titration curves start up higher with smaller K a values.
• the ½ titrated pH is at a higher pH because the acids are weaker, producing less hydrogen
ions.
• the equivalence point pH is higher because the conjugate base is becoming mor e basic as
the acid becomes less acidic.
(remember: the stronger the acid, the weaker its conjugate base so the weaker the weak
acid, the stronger its conjugate base)
• the over-titrated portion of the curve is the same for all acid analytes because all a cids are at
0.10 M so the titrant is always 0.10 NaOH.

Summary: pH Values for Decreasing K a Value at Constant Analyte Concentration of 0.10 M

Ka initial pH ½ way pH = pka eq pt pH 30 mL pH

10 mL 20 mL
1.0 × 10–2 1.5 2.0 7.5 12.52
1.0 × 10–4 2.5 4.0 8.5 12.52
1.0× 10–6 3.5 6.0 9.5 12.52

Titration Curves for Different Strength Acids Titrated with NaOH

16

14

12

10
pH

0
0 5 10 15 20 25 30 35
Volume NaOH added, mL

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 52

 B

http://wps.prenhall.com/wps/media/objects/3083/3157555/blb1703.html

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 53

Summary:
General Type Typical Titration Curve Features of Curve
Strong acid Titration of 0.100 M SA w ith 0.100 M SB -start with low pH of SA
and strong 12.0 -eq pt. pH=7
base 10.0 -end with high pH of SB
8.0

pH
6.0
4.0
2.0
0.0
0.0 5.0 10.0 15.0 20.0
Volume of 0.100 M SB (mL)
Strong base Titration of 0.100 M SB w ith 0.100 M SA
and strong acid -start with high pH of SB
12.0 -eq pt. pH=7
10.0 -end with a low pH of SA
8.0
pH

6.0
4.0
2.0
0.0
0.0 5.0 10.0 15.0 20.0
Volume of 0.100 M SA (mL)
Weak acid and Titration of 0.100 M WA w ith 0.100 M SB
strong base starts with a higher of WA
12.0 -eq pt. pH>7 (higher than 7)
10.0 -end with a high pH of SB
8.0
pH

6.0
4.0
2.0
0.0
0.0 5.0 10.0 15.0 20.0
Volume of 0.100 M SB (mL)
Strong acid Titration of 0.100 M SA w ith 0.100 M WB
and weak base 12.0
-starts with a low pH of SA
-eq pt. pH<7
10.0
-end with a lower of WB
8.0
pH

6.0
4.0
2.0
0.0
0.0 5.0 10.0 15.0 20.0
Volume of 0.100 M WB (mL)
Weak acid and Titration of 0.100 M WA w ith 0.100 M WB
weak base -starts with higher pH WA
12.0 pka _+ pH unit eq pt. pH~7
10.0 end with lower pH WB
8.0
pH

6.0 very difficult to do

4.0
2.0 buffer region
0.0
0.0 5.0 10.0 15.0 20.0
Volume of 0.100 M WB (mL)
NAIT2014

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 54

Mixtures of weak acids and weak bases - Buffers

Buffers contain WEAK conjugate acid – base pairs which resist pH change when strong acids and
bases are added.

Henderson–Hasselbach equation

Buffers require the presence of two components, a conjugate base – acid pair, for a solution to
resist pH change. Obviously the Ka expression can be used to calculate [H 3O1+] and thus pH.

 [conjugate base]
pH = pKa + log 
 [weak acid] 

Buffer preparation

Buffers need to be prepared for many lab applications to control pH at a specific value. This
requires that the buffer be prepared to have an acceptable buffer capacity. This requires that an
acceptable concentration of the weak base/weak acid pair be prepared at a ratio which enables a
specific pH to be maintained.

Failing to account for the effect of ionic strength can lead to a significant error in the reported
concentration of H3O+. For example, if the pH of a solution is 7.00 and the activity coefficient for
H3O+ is 0.90, then the concentration of H 3O+ is 1.11×10−7M, not 1.00×10−7M, an error of +11%.
Fortunately, when developing and carrying out an analytical method, it is more likely for controlling
pH than in calculating [H3O+]. As a result, the difference between the two definitions of pH rarely is
of significant concern.

Steps:

1. Determine the pH of the buffer required, volume and concentration required to maintain an
acceptable buffer capacity.

+_ 1 pH unit from pka

2. Choose a buffer pair that will buffer at the pH required within the pH = pKa ± 1.0 range

pka acetic acid = 4.76 CH3COOH/CH3COO - = good pair for pH of 4.76

capacity (3.76 - 5.76) A Conj B

NH3/ NH4 + = good pair of pH 9.2

pkb ammonia = 4.76 pOH = 4.7
pH= 9.24 B conj A
3. Calculate the concentration and amounts of each of the buffer components required
[B] and [BH +]
[HA] and [A -]

Ka = [H3O +] [A -] / [HA] Kb = [OH -] [BH +] / [B]

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 55

 Buffer preparation by partial neutralization

Neutralization of a weak acid with a strong base

Calculate the pH of a solution prepared by mixing 350.0 mL of a 0.150 M acetic acid solution
with 125.0 mL of a 0.200 M NaOH solution.

Note: the buffer must be prepared with the combination of each component of the buffer pair.
If the buffer concentration is prepared using 1 member of the pair then the addition of the
2nd member there will be a huge error in the ionic strength.
CH3COOH + NaOH ---> CH3COONa + H2O
HA A-

[CH3COOH]remaining = (350 ml HA x 0.150 mol HA/ L) _ (125 mL NaOH x 0.200mol NaOH/ L x 1 mol Ha/ 1 mol NaOH)

/
350 mL + 125 mL

= 0.0579 mol HA / L

[CH3COO-] = 125mL x 0.200mol NaOH/ L x 1 mol A- / 1 mol NaOH

/ = 0.0526 mol A- /L
350 mL + 125 mL

pH = pka (acetic acid) + log [A-] formed / [HA] remaining => 4.76 + log (0.0526M) / (0.0579M)
= 4.72

buffer capacity: 3.72 - 5.72

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 56

Neutralization of weak base with a strong acid

Prepare 1.00 L of a 0.150 M buffer at pH 4.68 using solid sodium acetate and 1.50 M HCl.

Note: the sodium acetate concentration will be reduced and the acetic acid increased as
the HCl is added. A problem with this approach is that the ionic strength will be increased
by the presence of NaCl. For many applications this may not be a problem.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 57

Determination of required reagents (mass and volume) for a given buffer

Calculate the mass of sodium acetate and volume of 1.5 M acetic acid needed to prepare 2.00 L
of a 0.150 M buffer at a pH of 4.68.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 58

Titration of Polyprotic Acids or Mixtures of Acids

Acids that can donate more than one proton per molecule
Strong acid: H2SO4
Weak acid: H2CO3
For most cases, assume protons are removed sequentially

The criteria for titrating two acids in a mixture independently are:

• the difference between the Ka values must be  104
• the weaker acid Ka must be  10–5

Sulfamic acid has a Ka = 1 × 10–1 and KH2PO4 has a Ka = 6 × 10 –8

• when a mixture of sulfamic acid and KH 2PO4 is titrated, the two acids should titrate separately,
first the stronger acid then the weaker acid because the difference in Ka values between the
two acids is 10 7 and the weaker acid Ka is less than 10 -5.

pH

mL NaOH

H2SO3 has Ka1 = 1.71 × 10–2 and Ka2 = 5.98 × 10–8

• when titrating this diprotic acid, each acid hydrogen would titrate separately because the
difference between the two Ka’s is 104 and the weaker acid hydrogen has a K a less than 10–5.

pH

mL NaOH

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 59

HCl has a Ka =  (strong) and H2SO3 has Ka1 = 1.71 × 10–2 and Ka2 = 5.98 × 10–8
• when a mixture of HCl and H2SO3 is titrated, the HCl and the first acid hydrogen of H 2SO3 will
titrate together because both have a K a value greater than 10 –5 but the second acid hydrogen
on H2SO3 will titrate separately because the difference is 10 4 and the Ka2 is less than 10 –5.

pH

mL NaOH

H3PO4: Ka1 = 7.11 × 10–3 Ka2 = 6.23 × 10 –8 and Ka3 = 4.55 × 10 –13

pH

mL NaOH

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 60

Fractional Composition of Polyprotic Weak Acids

Acid:
H2A H+ + HA- Ka1 = first proton removed
K1 = [H+][HA-] / [H2A]

HA- H+ + A-2 Ka2 = second proton removed

K2 = [H ][A ] / [HA-]
+ -2

Base:
A-2 + H2O HA- + OH- Kb1
HA- + H2O H2A + OH- Kb2

We know: KaKb = Kw How does this relate to a polyprotic acid?

Example: Carbonic Acid

H2CO3 H+ + HCO3- Ka1 = 4.35 x 10 -7

HCO3- H+ + CO3-2 Ka2 = 4.69 x 10 -11

CO32-(aq) + H3O+(aq) HCO3-(aq) + H2O (l) Kb1 = 2.13 x 10 -4

HCO3-(aq) + H3O+(aq) 2 H2O(l) + CO2(g) Kb2 = 2.30 x 10 -8

Ka1 Kb2 = Kw
Ka2 Kb1 = Kw

http://www2.iq.usp.br/docente/gutz/Curtipot_.html

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 61

Titration of Polybasic Compounds or Base Mixtures

The criteria are the same as those for the acids

• the difference between the Kb values must be  104
• the weaker base Kb must be  10–5

Na2CO3 has a Kb1 = 2.1 ×10–4 and Kb2 = 2.2 ×10–8

• sodium carbonate is found naturally in the environment
• titration of a Na 2CO3 sample, each equivalent of base would titrate separately and would take
the same volume, so

Na2CO3 + HCl → NaHCO3 + NaCl

NaHCO3 + HCl → “H2CO3” + NaCl

• in the environment, various combinations of sodium carbonate, sodium bicarbonate and

sodium hydroxide can occur and each possible combination has a unique titration curve so the
particular combination can be determined.
• the various combinations are:
Na2CO3 only
Na2CO3 and NaHCO3
Na2CO3 and NaOH
NaHCO3 only
• by using two end points, phenolphthalein and methyl red, each possible situation can be
determined.

In the space below draw the expected titration curves for Na2CO3 only and Na2CO3 with NaHCO3

12.0
Titration of 20.0 mL 0.1 M Na 2CO3 with 0.100 M HCl

10.0

8.0
pH

6.0

4.0

2.0

0.0
0.0 10.0 20.0 30.0 40.0 50.0
Volume of 0.100 M HCl (mL)
NAIT2014

The rate at which the pH changes is lower than that of a strong acid/ strong base titration. This
lower rate is due to the mixture of the salt of a weak base-strong acid and a weak base causing a
buffering effect.

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 62

Example: 1.000 g sample is analyzed for Na2CO3 and NaHCO3. The phenophthalein endpoint
took 13.57 mL of 0.0875 M HCl and the methylred took 30.13 mL. What is the %m/m of Na 2CO3
and NaHCO3?

MM: Na2CO3 = 106.0

NaHCO3 = 84.0

13.57 30.13
0.0875 M HCl added, mL

At 1st endpoint 1 mol HCl reacts with 1 mol Na 2CO3

Na2CO3:

NaHCO3:

pH

mL HCl
NAIT2014

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 63

 Acid Salt

Partially neutralized polyprotic acid

Can act as either an acid or a base - amphiprotic
[H+] a function of Ka (acting as an acid) and Kb (acting as a base)
Relative behavior with water will be determined by the relative magnitude of K a and Kb for the ion
considered.

The two possible reactions that HPO 42-(aq) may undergo after the salt dissociates in water are:

HPO42- (aq) + H2O (l) H3O+ (aq) + PO43- (aq) (i) Ka3 = 4.55 x 10^-13
HPO42- (aq) + H2O (l) OH- (aq) + H2PO4- (aq) (ii) Ka2= 6.23 x 10^8

Depending on which has the larger equilibrium constant, that ion will cause the solution to be acidic
or basic.

The value of Ka for equation (i) can be referenced and is found to be 4.55 x 10-13. We calculate the
Kb for equation (ii) above from the value of K a for its conjugate acid H2PO4-(aq)
Ka x Kb = Kw

Kb, HPO42- = Kw 1 x 10 ^ -14 / 6.23 x a0 ^ -8 = 1.61 x 10 ^-7

Ka,H2PO4-

and Kb, HPO42- =

1.61 x 10 ^ -7

This Kb value is more than 10 5 times larger than the Ka for HPO42-(aq). So reaction (ii) will
predominate over reaction (i) and the solution will be basic.
Acts as a acid
Ka2 = 5.98 x 10 ^ -8
HSO3 - + H2O H3O+ + SO3 2-

Acts as a base
HSO3 - + H2O OH - + H2SO3 Ka1 1.71 x 10 ^ -2 => Kb2 = 5.85 x 10 ^ -13

1. compare Ka2 to Kb2

2. Ka2 is larger => in water HSO3 - is acidic

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 64

 OH
Titration Calculations of Polyprotic Acids
C O
Maleic Acid H2M HOOC-CH=CH-COOH HC CH
C O
25 mL of 0.100 M H2M with 0.100 M NaOH
OH
Equivalence Point Volume:

0.025 L x 0.100 M H2M x 2 mol NaOH/ 1 mol H2M x 1 L NaOH/0.100 mol NaOH = 50 mL

The volume is to completely titrate the H 2M so the 1st H+ will require 25 mL and the 2 nd 25 mL

H2M H+ + HM- Ka1 = 1.3 x 10-2

HM- H+ + M- Ka2 = 5.9 x 10-7

Initial pH: since Ka1 > Ka2 (factor >10 4) only the 1 st ionization contributes to pH

Ka1 = [H+][HM -]
[H2M]
here we can’t assume H2M-x is the same, x is not small relative to H 2M

ie: H2M H+ + HM -

If we assume x is small [H+] = √ka x [H2M] = 0.011M which is ~10% of [H2M]

Need to solve using quadratic:

1st Midpoint: ½ equivalence volume

pH = pKa1 = 1.89

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 65

1st buffer region: NaOH + H2M HM- + H2O

A. Solve like a simple acid:

[acid]remaining =

[base]formed =

pH

B. Quadratic
When H2M dissociates it makes [HM -] + [H+] and [H2M] – [H+]

Ka should be:

1st equivalence point:

The salt HM- is in solution (it is amphiprotic) and we assume:

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 66

 2nd buffer region: HM- + NaOH M2- + H2O

[acid]remaining =

[base]formed =

pH =

2nd Midpoint = ½ equivalence point

of the second H+ vol = 37.5 mL
neglect Ka1 pH = pKa = 6.23

-log(5.9x10-7

2nd equivalence point:

weak base=Kb conj
M2- is the species in solution: M2- + H2O HM- + OH-

Base: Kb = Kw/Ka2 = [HM-][OH-]

[M2-]
25.00mL HM- x 0.100 mol HM- x 1mol M2- / 1mol HM-
[M2-] =
/ = 0.0333mol/L M2-
25.00mL acid + 50.00mL NaOH added

OH = square root of Kb [M2-]

1 x 10-14 / 5.9 x 10-7 = x2 / 0.0333

OH = 2.37 x 10 -5
pOH = 4.63 pH= 9.37
After 2nd equivalence point:pH is found from addition of excess base.

Some OH- comes from M 2- but we ignore

[base]formed = 2.00 ml NaOH x 0.100 mol/L NaOH
/ = 2.60 x 10-5 mol/L OH-
25.00mL acid + 50.00mL NaOH + 2.00mL excess

pOH = 2.59 pH= 11.4

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 67

quiz on march 19 from 59-67

Volume Titration of 25.0 mL 0.100 Maleic Acid with

pH
NaOH 0.100 M NaOH
0 1.52 14.0
5 1.74
12.0
12.5 1.89
20 2.49 10.0
24 3.27
25 4.06

pH
8.0
28 5.4
30 5.63 6.0
37.5 6.23
4.0
42 6.56
49 7.61 2.0
50 9.37
51 11.1 0.0
52 11.4 0.0 20.0 40.0 60.0
Volume of 0.100 M NaOH (mL)
60 12.1
NAIT2014

NAIT Coursepack #2786 Acid / Base (Neutralization) Titrations 68

 5. Electrochemistry and Redox Titrations
Terminology and fundamental concepts of electrochemistry

A redox reaction requires both half-cells to be present. The rate of oxidation equals the rate of
reduction. For example, for corrosion to occur the oxidation of a metal must be associated with
the reduction of some other substance such as:
Zn + Cu2+ ---> Cu (s) + Zn2+ (aq)

* The cell potential is found by E cell = E cathode – E anode

0 0 0

This is follows the IUPAC ruling which requires the potential to be determined as if E cell is a
measure of the reaction proceeding from left to right. Called the plus right rule.

What is the potential for this electrochemical cell? What is the overall reaction?
Fe3+ + e- ⇋ Fe2+ E0 = 0.771 Sn2+ + 2e- ⇋ Sn E0 = -0.14

Pt / Fe2+(1M), Fe3+(1M) // Sn2+(1M) / Sn

anode cathode
oxidation reduction

E not cell = -0.14V - 0.771V

Electrolytic ---> non spontaneous, Enot
= -0.911V cell is negative

Spontaneous ---> galvanic (voltaic)

Enot cell is positive
Nernst equation is used to calculate the galvanic voltage of a cell where the concentration of the
reactants and products are known and are not at the standard concentrations found in reduction
potential tables.

For the chemical equation: a Ox + ne- ⇾ b Red

the Nernst equation is:

E = E0 - 2.3026 RT log [Red]b

nF [Ox]a

where: R = gas constant T = absolute temperature (K)

n = number of electrons F = Faraday constant ( 96500 coulombs/equiv)

@250C the Nernst equation is:

* E=Enot - 0.0

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 69

 Since most electrochemical reactions are monitored with a reference ½ reaction which stays
constant, only one ½ reaction will change. As a result, the E for the measured reaction is
usually determined in measurements relative to a constant reference ½ cell.

Write the Nernst equation expression for the following ½ reaction:

MnO4- + 8H+ +5e- ⇋ Mn2+ + 4H2O E0=1.51 V reduction 1/2 half reaction
[Mn2+] = 0.1 M, [MnO4-] = 0.05 M and [H+] = 0.2M

E= 1.151V - 0.0592 / 5 log ( 0.1M) / (0.05M)(0.2M)^8

E= 1.44V

Which species in the above reaction is undergoing reduction?

Notice that when the concentrations of species in the log term are 1.0 M, the E=E 0. The Nernst
equation is used when these concentrations are not at standard conditions.

Factors which influence Nernst equation:

Concentration:as concentrations change the log term becomes effected. If an ion is affected by any
equilibria (solubility, complexation) its concentration will decrease and the reduction potential
becomes affected.
standard conditions: IM, 1atm, 25 celcius
Effect of Ksp: What is the potential for a silver wire in a solution which is 1.0 M I 1-
AgI (saturated), I 1- (1.00M)/ Ag
I- + Ag+ --> AgI (s) Ksp 8.3x 10 -17
Ag + e- --> Ag(s) Enot = 0.799V
<---
std conditions [I-] = 1M so [Ag] = Ksp
E=Enot - 0.0592/n log 1/ [Ag+]
Ksp = [Ag+] [I-]
Ksp = [Ag+] [1.0M]
= 0.799V - 0.0592/1 log (1/8.3 x 10-17)

Do the standard reduction potentials for Ag, AgCl, AgBr, and AgI indicate this effect?

Activity: When other ions are in solution (spectator ions), the ionic strength of the solution is
affected. This in turn affects the concentration of the analyte ion. Nernst equation calculations
should be done with activities.

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 70

Applications in potentiometric titration
http://www.titrations.info/potentiometric-titration-curve-calculation

Requirements of redox titrations

1. The potential difference between the titrant and analyte half-reaction should be 0.2 to 0.3 V for
a sharp end point in a redox titration.

2. Adjustment of analyte oxidation state. Usually the titrant is an oxidizing agent therefore the
adjustment of the oxidation state of the analyte involves a reduction. The reducing agent used
cannot remain. The reducing agent is often contained as packing within a column - a metal
reductor column (Zn (Jones reductor) or Ag (Walden reductor)). Sample is passed through the
column to effect reduction.

3. Common oxidizing agents:

KMnO4
K2Cr2O7
I2
KI
KBr

4. Common reducing agents:

Fe2+
Sn2+
As2O3
Na2S2O3
Hg₂(NO₃)₂
CrCl2
CrSO4

Calculations of Redox Titrations

For a reaction A + B goes to products:

Pre-equivalence point E is found using titration data

n A E A0 + EB0 nB
Equivalence point can be found usingEeq = (in most simple reactions)
n A + nB
Post equivalence point E can be found using the titrant’s Nernst expression.

A titration of 50.0 mL of 0.0500 M Fe 2+ with 0.100 M Ce 4+in 1 M sulfuric acid.

Fe2++ Ce4+ → Fe3+ + Ce3+

The cell can be shown as SHE││ Ce 4+, Ce3+, Fe2+, Fe3+ │Pt

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 71

 The initial potential is found using the Nernst equation for the ferrous ½ reaction:

After the equivalence point the potential is found using the Nernst equation for the ceric ½
reaction:

NOTE: in this titration the standard potential is given in a specific solvent which affects the E 0, this
standard potential is called the formal potential.

First find the equivalence point vol:

Before eq pt; Find the E after 5.0 mL of 0.100 M Ce 4+ is added

[Fe2+] remaining is:

[Fe3+] formed is:

E = E0 −

0.0592  Fe 2+
log
 =
n 
 Fe
3+


NAIT Coursepack #2786 Electrochemistry and Redox Titrations 72

 Other points before the equivalence point on the titration curve are found similarly.

The equivalence potential can be found by

𝑛𝐴 𝐸𝐴𝐹𝑒 + 𝑛𝐵 𝐸𝐵𝐶𝑒
𝐸𝑒𝑞 =
𝑛𝐴 + 𝑛𝐵

Post equivalence point potential; when 25.10 mL of 0.1 M Ce4+ is added.

The potential is found from determining ceric and cerous ion species;
need the concentration of Ce 3+ formed:

need the concentration of Ce 4+ excess:

The potential is now found from:

E = E0 −

0.0592  Ce3+
log
 =
n 
 Ce
4+


NAIT Coursepack #2786 Electrochemistry and Redox Titrations 73

Electroanalytical Applications

Redox indicators

Specific:

1. starch as an indicator in iodine titrations

Iodine is an oxidizing agent. As triiodide, it is used for the analysis of arsenic, tin and sulfur
containing compounds.

Iodimetry -the analyte is a reducing agent and the titrant is I2. The end point is
determined by the appearance of the blue starch-iodine color.

H2S + I2 ⇋ S + 2I1- + 2H1+

Iodometry -the analyte is an oxidizing agent that reacts with I1- to form I2. The I2 is titrated
with thiosulfate. The disappearance of the starch-iodine color is used as the endpoint.

Cr2O72- + 6 I1- (excess) + 14H1+ ⇋ 2Cr3+ + 3 I2 + 7 H2O

I2 + 2 S2O32- ⇋ 2 I1- + S4O62-

Procedural considerations: Starch is added near the end of the titration when the dilute I 2
color becomes a pale yellow.
• iodine-starch complex dissociates slowly which would result in a diffuse endpoint if the
starch were added when the iodine concentration was high.
• An acidic medium is commonly used to promote the reaction between the oxidizing
agent and iodide. These conditions promote the hydrolysis of starch and the loss of the
helical structure of the starch.
I2 will readily oxidize in oxygen and light.

In the analysis of S as SO 2(g), the SO2(g) reacts with iodine produced by a side reaction.

2. Permanganate as a self-indicating reagent.

an oxidant used for the determination of iron, hydrogen peroxide, arsenic, oxalic acid and
many others

A solution of KMnO4 ranges from a faint pink to a deep purple and functions as an oxidizing
agent in these types of redox titrations.
The product of KMnO4 reduction is Mn 2+, which is nearly colorless. Mn2+ is formed during
the titration of the analyte.
When the analyte has completely reacted, the first drop of KMnO 4 over the end point will
cause a definite pink color to remain in the solution.
This occurs after the equivalence point but can be corrected by running a blank or
accounting for it during standardization of the KMnO 4.
KMnO4 is standardized by using sodium oxalate (Na 2C2O4) as the primary standard. The
sodium oxalate is dissolved in acid which converting it to oxalic acid.

5 H2C2O4 + 2 MnO41- + 6 H1+ ⇋ 2 Mn2+ + 10 CO2 + 8 H2O

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 74

 Procedural considerations: The solution is heated during the reaction to speed up the
reaction. The reaction is slow until Mn 2+ is formed. Mn 2+ will catalyze the reaction.
KMnO4 will readily oxidize organics. Prepared solutions must be boiled or stored for
several days for existing organics to oxidize then filtered through sintered glass to remove
particulates (oxidized material will promote further oxidation). The solution is then stored in
a dark or covered reagent bottle to prevent oxidation with light.

General Redox Indicators

As with other indicators, the colour change must occur very close to the equivalence point
potential of the reaction. The indicator will exhibit different colours in the different oxidation
state.

methylene blue (blue when oxidized, colourless when reduced)

4'-ethoxy-2,4-diaminoazobenzene (yellow when oxidized, red when reduced)
diphenylamine (violet when oxidized, colourless when reduced)

Electrolysis: electrolytic process where the movement of an electric current through an ion-
containing solution produces chemical changes at the electrodes.

Electrodeposition A common application where an analyte ion is deposited on an electrode.

Faraday’s Laws of Electrolysis are used to determine quantities and current efficiencies.

By definition:
1 Faraday = 1F = 1 equivalent of e - = 96500 Coulombs
1Coulomb (C) = 1 Amp-sec
The charge in electrolysis is determined from the current and time. This charge (Coulombs) can
then be used to determine the above mentioned variables.

Example: If a current of 0.200A is applied for 60 min and 48 seconds to an aqueous copper
solution, determine the grams of Cu plated and liters of oxygen produced at STP (760 mm Hg and
0 C). Why is the applied potential for this electrolysis greater than 1 V?

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 75

The properties of a deposit are a fine grain with a metallic luster. Spongy, powdery, flaky
precipitates are less pure and less adherent. The physical characteristics are affected by
competing electrode processes, current density, temperature, and stirring.

Gas evolution: results in spongy irregular deposits. With cathodic reactions hydrogen gas (2H 1+
+ 2e ⇋H2 E0 = 0.000 V ) can be prevented by using a depolarizer ( nitrate). The addition of
the nitrate ion (which reacts with H +) controls gas formation and itself is more difficult to
reduce than Cu2+.

Current density: keeps crystals small. Moderate current density usually gives good precipitates.
High currents produce localized growth and side reactions (gas formation). Use of large
surface electrodes and low currents are helpful.

Concentration polarization: mechanical agitation such as stirring helps reduce concentration

polarization, by transporting the electroactive species.

Temperature: temperature effects can have profound effects on the deposit. The operating
temperature has to typically be found empirically.

Chemical variables:
• pH- used to selectively remove other metal ions in the presence of others
• complexing agents: metals usually precipitate better in the presence of complexing agents,
though higher potentials are needed.

NAIT Coursepack #2786 Electrochemistry and Redox Titrations 76

6. Complex Formation Titrations
Applications of coordination chemistry

Coordination chemistry examines the bonding of metal ions to lone pair electrons of ions or
molecules (ligands) that surround the central metal ion. These coordination complexes are also
called complex metal ions. An example is the bonding of EDTA to Ca 2+.

Has donating e- species by a coordinate covalent bond

metal = lewis acid = accepts e- pair

ligand = lewis base = donates e- pair

EDTA
means
to bind
where do all e- pairs go?
d orbitals

off axis: dxy dxz dyz

on axis: dz^2 dx^2 -y^2

Some of the applications of coordination chemistry are:

• Chelating agents (e.g. antidotes for heavy metal poisoning, titrimetry, masking agents in
instrumental analysis)
ex EDTA: as Na2 salt - deto metals Hg, As, Pb
soften dentin- for root canals

ligands and chelons to mask interfering metal ions: fluoride ion to mask iron, tartaric acid to
mask aluminum

• Biomolecules compounds (e.g. chlorophyll, hemoglobin, vitamin B12, enzymes)

• Catalysts

• Medical (eg. Drugs and anticancer agents)

• Chemical analysis (e.g. spectrophotometric methods of analysis due to the colour of complex
metal ions - Fe-bipyridine complex. Colour can vary depending on the nature of the ligand.
- liquids effect interactions with light

• Effects on the solubility of precipitates – increase solubility

AgCl(s) - relatively insoluble - if [Cl-] increases can get soluble

comples like AgCl2 - or AgCl3 2-
• Coloring agents (e.g. ink, paint, eyeshadow)

NAIT Coursepack #2786 Complex Formation Titrations 77

Terminology

Ligand is a Lewis base (electron donor) that bonds with the metal ion. The electron pair used for
bonding is viewed as a tooth (“dent” in latin). A ligand that can bond to a metal in two or more
positions (polydentate) as if with a ”claw”; Greek, chelos, is called a chelating agent.

• Monodentate (one tooth) ligands are capable of donating a single pair of electrons to a metal
atom. Examples are: F 1-, Cl1-, Br1-, I1-, H2O, NH3, OH1-, CO, CN1-, SCN1-

• Bidentate ligands are capable of donating two pairs of electrons to a metal ion. Examples are:
2,2'-bipyridine 1,10-phenanthroline

• Polydentate ligands are capable of donating multiple pairs; 3, tridentate; 6, hexadentate.

EDTA is a hexadentate ligand which is one of the most common chelating agents.

The Process of a Metal Ion Bonding to its Ligands

• the process of a metal ion forming bonds to its ligands is a stepwise set of equilibrium
reactions.
• the formation of Ag 1+(aq) would proceed as :

Ag1+ + H2O Ag(H2O)1+ equilibrium formation constant = Kf1

Ag(H2O) 1+ + H2O Ag(H2O)21+ equilibrium formation constant = Kf2

• there is an equilibrium constant called the formation constant (K f ) for each step, i.e. for each
equilibrium reaction that adds another ligand to the metal.
• the overall formation constant is the product of all the individual formation constants, so the
overall formation constant for the Ag(H 2O)21+ would be: Kf = Kf1 × Kf2

Complex Ions

• a metal ion without any ligands would be referred to as a simple metal ion or an
uncomplexed metal ion and would be very unstable.
• the ion produced when a simple metal ion combines with ligands is called a complex ion.
• when the ligands are neutral, then the complex ion of the metal will have the same charge
as the simple metal ion.
• when the ligand has a negative charge, the complex ion of the metal will have a different
charge than the simple metal ion; the complex ion of the metal may even be negative!!!

i.e.: Ag1+ with neutral water, Ag(H2O)21+ and Ag1+ with negative CN1–, Ag(CN) 21–

NAIT Coursepack #2786 Complex Formation Titrations 78

Stability of the complex ion

• the formation of a complex metal ion makes the metal ion more stable than the simple
metal ion would be.
• the larger the formation constant Kf , the more stable the complex ion.

Ag(NH3)21+ Kf ~1.7 × 107 dicyanosilver complex ion is much more

Ag(CN) 21– Kf ~ 1 × 1020 stable than the diamminesilver complex ion

• when comparing two ligands, the ligand that would produce the more stable complex ion
would be referred to as the stronger ligand, i.e. CN 1– is a stronger ligand than NH 3.
• when two ligands compete for the same metal ion, the ligand that produces the more stable
complex ion will form the final product; the stronger ligand will form the product.
• when a complex ion is already formed and an alternate ligand is introduced in to the
solution that can form a more stable complex ion, then the stronger ligand will displace the
weaker ligand so that the more stable complex ion is formed.

Ag(NH3)21+ + 2 CN1– Ag(CN) 21– + 2 NH3

• the cyanide ligand is a stronger ligand than the ammonia ligand because the complex ion
formed with cyanide is more stable, has a higher formation constant, than the complex ion
formed with ammonia: 1 × 10 20 >> 1.7 × 10 7
• the equilibrium reaction shows the cyanide ligand displacing the ammonia ligand from the
diamminesilver complex ion.

Coordination Numbers

The formula of a complex ion is written with the central metal atom first followed by the ligand(s).
This complex ion is written within square brackets and other components are written outside of the
brackets. The coordination compound: [Cu(NH 3)4]SO4 consists of Cu(NH3)42+ as the complex
cation and SO42- as the anion in the salt.

The metal ions used to form a complex with ligands must have d orbitals available for bonding.
Thus most complexes are formed with the metal ion from the transition elements.

The coordination number indicates the number of electron pairs donated to the central metal ion.
Thus determines the geometry of the complex.

The table below contains complex ions formed with several coordinatio n numbers. The geometry
of the complex ion is determined by the coordination number.

NAIT Coursepack #2786 Complex Formation Titrations 79

Geometry of complex ions with different coordination numbers based on VSEPR

Coordination Metal Ion

Geometry Example
number in Solution

2 Ag+(aq) L M L [Ag(NH3)2]1+
linear

L
[Cu(Cl) 4]2-
Ni+2(aq)
4 M
Cu+2(aq)
L L
L
tetrahedral

L L [Cu(OH2)4]2+
Co+2(aq)
4 M
Cu+2(aq)
L L
square planar

L
Fe+2(aq) L L [Fe(OH2)6]2+
Fe+3(aq)
6 M
Mg+2(aq)
Ca+2(aq) L L
L
octahedral (most common)
M = metal ion; L = ligand atom NAIT2014

Naming Coordination Compounds

Rules for writing coordination compounds:

• Identify the cation(s)

• Determine the charge of the anion (for a neutral compound) using the charge and number of
cations
• Deconstruct the anion by determining the ligands, anions and cations. Determine the charge of
the ligand and anions to get the charge of the metal ion.
• Name each part of the compound:
Ligand – add an ‘o’ to the root of anions ending in –ide.
Neutral ligands normally use the name of the molecule the exceptions are
below.
See the table below for the names of common ligands.
Use Greek prefixes mono, di, tri, tetra, penta and hexa to indicate the
number of ligands present.
When more than one ligand is present list them in alphabetical order (do
not use the prefixes).
Metal ion – indicate the oxidation number of the metal using Roman numerals in
parenthesis or use the Latin names found below
If the compound is negatively charged the metal ion name changes to –
ate.

NAIT Coursepack #2786 Complex Formation Titrations 80

 • Put it all together:
cation – complex ion (neutral before anionic ligands) placed in square brackets – metal ion
complex ion (neutral before anionic ligands) placed in square bracket s – metal ion - anion

Names of some common ligands:

Neutral Ligands Anionic Ligands Latin names for some metal
anions
H2O Aqua F- Fluoro Iron Ferrate
NH3 Ammine Cl- Chloro Copper Cuprate
CO Carbonyl Br- Bromo Lead Plumbate
NO Nytrosyl I- Iodo Tin Stannate
OH- Hydroxo Gold Aurate
CN- Cyano Silver Argentate
complex ion NO2- Nitro Cobalt Cobaltate
-1 x 2
Name: [Co(NH3)5Cl]Cl2 Name: K3Fe(CN) 6 CN -1
Charge of = charge of - total charge Charge of = charge of - total charge
metal ion complex ion of all ligands metal ion complex ion of all ligands
+2 (5xo)+ (1x-1) Fe(CN)6 -3 CN -1 x 6
Fe
NH3 Cl-
-1 +3 = -3 subtract from -6

+3 = +2 - (-1)
iron(III)
=> Co3+ or Cobalt (III)
ferrate(III)
5NH3 ligands -> pentaamine
1Cl - -> chloro
6 CN - ligands --> hexacyano
complex ion: pentaamine chlorocobalt (III)
complex iron: hexacyanoferrate(III)

counter ion: chloride

counter ion: potassium
[Co(NH3)5Cl]Cl2 -> pentaamine chlorocobalt(III)chloride
potassium hexacyanoferrate(III)
Name:[Fe(en) 2(NO2)2]2SO4 (en=ethylenediamine)

[Ag(NH3)2]+

[Ag(CN) 2]-

K2[Co(NH3)2Cl4]

Write the formula for triamminebromoplatinum(II) chloride

metal
[Pt+2(NH3)3Br-1]Cl => [Pt(NH3)3Br]Cl
platinum
+2 +2 + -1 = 1
NAIT Coursepack #2786 Complex Formation Titrations 81
Bonding in metal complexes

a. Valence bond theory

In valence bond theory the ligand bonds via a coordination covalent bond where the ligand atom
furnishes the electron pair. The hybridization of the metal ion determines the geometry of the
complex. Therefore, the number of ‘d’ electrons the metal has is required for understanding which
orbitals are available for bonding.
Number of 'd' electrons = group number - charge of the metal

ex: Ag +1 : 11 - (+1) = 10 d electrons

Example of a metal ion with a coordination number of 2; [Ag(NH 3)2]1+

Silver Atom
[Kr] 4d105s1

5d
5p
[Kr] 5s
4d
Ag1+ ion
[Kr] 4d10

5d
5p
[Kr] 5s hybridization
4d - hybrid orbitals must be empty to accept ligand e -
Ag1+ ion sp hybridization
[Kr] 4d10

NH3 NH3 5d
5p
[Kr] 5sp
4d hybridization

1+ linear geometry
H3N Ag NH3
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NAIT Coursepack #2786 Complex Formation Titrations 82

 Example of a metal ion with a coordination number of 4; [Cu(Cl) 4]2-

4 Cl ligand ions
Copper Atom
[Ar] 3d104s1

4d
4p
[Ar] 4s
3d 2e- lost
Cu2+ ion
[Ar] 3d9

4d
4p
[Ar] 4s
3d
Cu2+ ion sp hybridization provides 4 orbitals - > Sp3 hybridization
[Ar] 3d9

Cl Cl Cl Cl 4d
[Ar]
4sp3
3d hybridization
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lone e - , so it is expected to be magnetic

if there is one or more unpaired electrons the material is paramagnetic

* if all e - are paired the material is diamagnetic (repelled by a magnet)

- most complexes having 4 ligands (donor species) are tetrahedral

- very few are square planar

NAIT Coursepack #2786 Complex Formation Titrations 83

Example of a metal ion with a coordination number of 6; [Cu(OH 2)6]2+

Copper Atom
[Ar] 3d104s1

4d
4p
[Ar] 4s
3d
Cu2+ ion
[Ar] 3d9

4d
4p
[Ar] 4s
3d hybridized orbitals sp3d2
Cu2+ ion sp3d2 hybridization
[Ar] 3d9
H H H H H H
H O H O H O H O H O H O 4d
[Ar]
4sp3d2
3d hybridization
NAIT2014

lone e- => paramagnetic

NAIT Coursepack #2786 Complex Formation Titrations 84

 hexaaqua iron(III)
Example of a metal ion with a coordination number of 6; [Fe(OH 2)6]3+

Iron Atom
[Ar] 3 3d6 644s22

4 4d
4p
[Ar] 4s
-
3d
lose 3 e-
Fe3+ ion
[Ar] 3 3d5 5

6 4d
4
4p
[Ar] 4s
3d hybridization
Fe3+ ion sp3d2 hybridization
[Ar] 33d55

5 H H H H H H
H O H O H O H O H O H O 4d
[Ar]
4sp3d2
3d hybridization
NAIT2014
paramagnetic
b. Crystal field theory

The valence bond theory can explain many structural and magnetic properties of coordination
compounds. Most of the metals have unpaired electrons in atomic orbitals which account for the
paramagnetic properties of the metal complex.

However, some structures would be expected to be paramagnetic (some electrons with unpaired
spins) based on valence bond theory but are diamagnetic indicating paired electrons in the atomic
orbitals. Additionally, the numerous colours of metal complexes for the same metal io n suggest
that the valence bond theory is inadequate to explain all properties of coordination compounds.

The magnetic properties of complexes can be assessed with a magnetic susceptibility balance.

http://en.wikipedia.org/wiki/File:Gouy_bal.png

NAIT Coursepack #2786 Complex Formation Titrations 85

Valence bond theory state that electrons from the ligand atom are shared with a metal ion orbital
forming a coordinate covalent bond. However, in crystal field theory the electrons on the ligand
atom stay with the ligand and electrons on the metal ion stay with the metal ion. The theory
explains the effect of ligand electrons on the d electrons of the metal ion. To understand these
effects the orientation of the d atomic orbitals of the metal ion must be understood.

http://en.wikipedia.org/wiki/File:D_orbitals.svg

Ligands in order of increasing crystal field strength

I1- < Br1- < Cl1- < F 1- < OH1- < H2O < (COO) 22- < NH3 <en< NO21- < CN1-

Weakest Strongest

This order is also known as the spectrochemical series. Since a stronger ligand splits the
field more (larger Δ) there will a decrease in the wavelength for absorption (more energy).

The observed color is related to the energy needed to promote an elec tron. A shorter
wavelength transmitted (e.g. green) is caused by the absorbance of a longer wavelength
where less energy is needed to promote the electron.

NAIT Coursepack #2786 Complex Formation Titrations 86

c. High and low spin octahedral configurations and ligand field strength

An octahedral complex forms with the electrostatic interactions occurring along the dx2-y2, dz2.
Electrons are repelled as the ligand approaches causing the dx2-y2, dz2 electrons to split to a higher
energy.

a. Fe2+ in the presence of a weak field ligand

High spin complex:

NAIT2014

• Crystal field splitting and electron pairing energy

Rule: If splitting energy,  octahedral, is < pairing energy (energy to cause electrons to
pair) a high spin complex exists. The number of unpaired electrons is the same as
when the metal is uncomplexed.

• Magnetism- the unpaired electrons cause this to be paramagnetic.

• Color
The color wheel depicts the spectral color (color absorbed) and the complementary
color (color observed). For example, if a metal complex absorbs violet (short
wavelength – high energy) the color observed will be yellow, the color transmitted.

Wavelength color absorbed and color observed

Wavelength (nm) Spectral color (color Complementary color
absorbed) (color observed)
410 violet lemon yellow
480 blue orange
530 green purple
560 yellow violet
610 orange blue
680 red blue-green

NAIT2014

NAIT Coursepack #2786 Complex Formation Titrations 87

 b. Fe2+ in the presence of a strong field ligand
Low spin complex:

NAIT2014

• Crystal field splitting and electron pairing energy

Rule: If splitting energy,  octahedral, is > pairing energy (energy to cause electrons to
pair) a low spin complex exists. The number of unpaired electrons is NOT the same
as when the metal is uncomplexed. The electrons pair with electrons in the lower
energy set, dxy , dxz , dyz , before pairing with the higher energy, dx2-y2, dz2, orbitals.
Since the metal complex would have fewer unpaired electrons than the metal atom a
low spin complex exists for the metal and ligand.

Metal ions with d4, d5, d6 and d7 configurations are capable of different low and high
spin configurations.

• Magnetism –electrons are all paired resulting in a diamagnetic system.

The effect of the spectrochemical series can also be seen in Cobalt complexes.

Co 3+ complex [CoF 6]3- [Co(NH3)6]3+ [Co(CN) 6]3-

Wavelength of absorbed light, nm 700 475 310
Colour of absorbed light red blue Ultraviolet

Spin high low low

Colour observed green yellow-orange pale yellow
NAIT2014

NAIT Coursepack #2786 Complex Formation Titrations 88

5. EDTA titrations of metal ions at variable pH

O O
HO C CH2 CH2 C OH

N CH2 CH2 N

HO C CH2 CH2 C OH

O O

Formation Constant

The basic form of EDTA, Y4-, reacts with metal ions in a 1:1.

Reaction:

Equilibrium expression for the formation constant, K f

• EDTA is a tetraacid, so short-hand notations are: H4EDTA or H4Y

• the Ka values = 1.02 × 10 –2 , 2.14 × 10 –3 , 6.92 × 10 –7 , 5.5 × 10 –11
the pKa values = 1.99, 2.67, 6.16, 10.26
• the form of EDTA in solution depends on the pH of the solution: if pH is 3 -6 then you would
have mostly H2Y2– , at pH 9, mostly HY3–.
• EDTA is purchased as the Na 2EDTA (i.e. the disodium salt of the tetraacid) because this
salt is more soluble in water.
• EDTA reacts with metal ions by forming a cagelike structure around the metal ion
essentially isolating the metal ion from the water molecules; this com plexation has very high
formation constants, i.e. the chelate complex is very stable, so EDTA can displace all other
simple ligands, i.e. H2O, and most other chelons as well.
• the EDTA complexing reaction occurs in one step producing a very large change at the
equivalence point.
• the EDTA complexing reaction reacts in a 1:1 mole ratio with all the metals.
• when EDTA reacts with the metal ion, EDTA looses all four acid hydrogens and reacts in the
form of Y4– or EDTA4–
• because the EDTA looses acid hydrogens in the complexation reaction, H1+ is a product
which makes the complexation reaction pH dependent.

at pH 9-10: HEDTA3– + Ca2+ → EDTACa2– + H1+

• because the reaction is pH dependent, a buffer must be added to the reaction solution to
maintain the pH at a particular pH value; if the reaction pH becomes too low, the
complexation reaction changes from an irreversible reaction to an equilibrium reaction
which would be useless for a quantitative analysis.
• each metal ion has a minimun pH value that must be maintained so that the complexation
reaction remains irreversible (quantitative); the graph below illustrates this.

NAIT Coursepack #2786 Complex Formation Titrations 89

 Effective formation constant (at a given pH):

Minimum pH for effective titration of metal ions

Christian, Gary, Analytical Chemistry, John Wiley & Sons, 6th Edition, 2004

Effect of pH on EDTA Titration of Ca2+

10
9
8
7
6
pCa 5
4
3
2
1
0
0 10 20 30 40 50 60 70 80
Volume EDTA, mL

pH = 6.0 pH = 7.0 pH = 10.0

NAIT Coursepack #2786 Complex Formation Titrations 90

What pH should be chosen so that an EDTA titration of a mixture of copper and manganese results
in only Cu ions being titrated? …. Both ions titrated?

A 50.00 mL aliquot of a solution having Fe 2+ and Fe3+ required 13.73mL of 0.0120M EDTA at pH
2.0 the analyte pH was adjusted to pH 6.0 and further titrated to a total volume of 29.62mL. What
are the molar concentrations of Fe 2+ and Fe3+?

EDTA titration indicators

Similar to other indicators, metal ion indicators will have one colour when it is uncomplexed and
another colour when it is complexed.
• Often they have properties similar to acid-base indicators so pH of the sample becomes
important.
• the indicator will initially bind to the metal and as the titration proceeds, the EDTA will have
to bind with that metal. This means that the indicator must be more weakly bound to the
metal than the EDTA

Common metal indicators:

• calmagite – at pH 10 complexed is red and uncomplexed is blue
• xylenol orange – at pH 1-6 complexed is orange and uncomplexed is yellow

Auxiliary complexing agents or masking agents

When samples have other metals in solution that are not the desired analyte, a masking agent
can be added. A masking agent will bind so tightly to the interfering metal that the EDTA
cannot react with it.
• CN- is a strong ligand and at pH 10 will form complexes with several metals (Zn2+, Hg2+
Co2+,Cu+, Ag+, Ni2+ Pd2+ Pt2+ Fe2+ and Fe3+) it will not complex with other metals
(Mg2+,Ca2+, Mn2+ or Pb2+)
• ascorbic acid, at pH 2 will mask Cu 2+, Fe2+ and Hg+ but not Bi2+ and Th2+

NAIT Coursepack #2786 Complex Formation Titrations 91

EDTA titration for calcium ion

• the titration curve for an EDTA titration has the same general shape as the acid/base
titration curves; the length of the vertical equivalence point is quite large if the correct pH is
maintained.
• there are two indicators that can be used for the EDTA titration; both are chelons:
HO
OH
HO
OH
N N SO 3 H

N N SO 3 H

NH2
Calmagite Eriochrome Black T ( EBT, H3EBT )

the analyte is Ca 2+(aq)

the titrant is the chelon, EDTA
the indicator is EBT.
• a small amount of magnesium ion, Mg 2+(aq), is added so that the indicator has a sharp
colour change; at pH 10 the indicator is either complexed as EBTMg 1– = red or is in the
free form EBT 3– = blue.
• during the titration, the titrate contains Ca 2+(aq), Mg2+(aq), EBT indicator chelon and EDTA
titrant chelon.
• the stability of the 4 possible chelate complexes are:
EDTACa2– > EDTAMg2– >> EBTMg1– > EBTCa1–

• the stability order means that EDTA will preferentially react with calcium ion in any form
because the EDTACa chelate complex is the most stable complex which is good because
this means the titrant will react with the analyte no matter what is the the titr ate solution with
the calcium.

pH = 10
• analysis reaction is: HEDTA3– + Ca2+(aq) EDTACa2– + H1+
pH = 10
• indicator reaction is HEDTA3– + EBTMg1– EDTAMg2– + EBT 3– + H1+
red blue
Before the Equivalence Point
pH = 10
HEDTA3– + Ca2+ + EBTMg1– EDTACa2– + Ca2+ + EBTMg1– + H1
red red

• EDTA reacts preferentially with Ca 2+ so no change to EBTMg 1– indicator, no colour

change, stays red

Reaching the Equivalence Point

pH = 10
HEDTA3– + Ca2+ + EBTMg1– EDTACa2– + EBTMg1– + H1
red red

• all Ca2+ reacted and no Ca 2+ or EDTA left in titrate solution.

• EBTMg1– indicator unaffected, no colour change, still red.

NAIT Coursepack #2786 Complex Formation Titrations 92

 After the Equivalence Point

pH = 10
HEDTA3– + EBTMg1– EDTAMg2– + EBT 3– + H1+
red blue

• overtitrated: EDTA now reacts with the Mg 2+ ion

• EDTA displaces the Mg 2+ ion from the indicator to produce the more stable EDTAMg 2-
• loss of the Mg 2+ ion from the EBTMg 2- indicator leaves uncomplexed indicator, EBT 3– so the
colour changes to blue, the end point colour.

Conclusion

• there is an over-titration required to observe the indicator colour change.

• since a blank can not be set up easily, standardize and analyze in exactly the same way so
the determinate over-titration error cancels.
• an ammonia / ammonium ion buffer is used to maintain pH 10 so that both the indicator
reaction and the analysis reaction are quantitative (irreversible).

NAIT Coursepack #2786 Complex Formation Titrations 93

Titration examples:

Direct Titration:

Zn in 0.7162g sample of foot powder was titrated with 21.27mL of 0.01645M EDTA. Calculate %
Zn in the sample.

Back titration

A 2.40g sample is diluted to 250.0mL. A 25.0mL aliquot has 30.0mL of 0.0100M EDTA added to
complex the Al3+. The excess EDTA required 8.0mL of 0.0100M Zn 2+. Determine the % Al in the
sample.

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8. Gravimetric Analysis
Method of quantitative analysis
Analyte is converted to a solid substance of known composition and separated from the sample

Common steps of gravimetric analysis:

1. Analyte Preparation

As discussed in the sample preparation at the beginning of the semester. The sample
containing the analyte must be in solution form. Other reagents may be added to ensure the
analyte is in the correct oxidation state.

Ex:

2. Precipitation

Properties of Precipitates

The two objectives of all the steps of a gravimetric procedure are:

Desirable properties of precipitates

1. quantitative precipitation:

2. pure in weighed form

3. precipitate is large crystalline particles

4. known and constant composition

NAIT Coursepack #2786 Gravimetric Analysis 95

Mechanism of Precipitate (Crystal) Formation

1. add precipitating agent to produce a supersaturated solution of precipitate.

• supersaturated solution contains more precipitate than maximum solubility, so excess
solute wants to come out of solution, i.e. precipitate.

Relative Supersaturation Ratio - (RS or von Weimarn Ratio)

• relative supersaturation ratio: describes particle size during precipitation,

(Q - S)
RS = RS = the degree of supersaturation
S
• S = equilibrium concentration or maximum solubility of the precipitate
• Q = supersaturation concentration, concentration just before precipitation
• (Q-S) = amount of supersaturation, i.e. the amount that will precipitate

Ex if max solubility (S) is 0.10 M and concentration just before precipitation is Q = 0.15 M

Ex if Q = 0.20 M

So • if RS is a large value, the result is many very small crystals or a colloid with a very large
surface area because the crystallization process is very fast i.e. goes for more
nucleation sites strategy. This is the undesirable strategy.
• if the RS is a small value, the result is fewer large crystals with a smaller surface area
because the crystallization is a slow process i.e. goes for grow existing crystals larger
strategy. This is the desirable strategy.

GOAL: during the precipitation process, keep the relative supersaturation ratio small and to
accomplish this, analytical procedures need to keep the value of Q low and the value of S
large.

NAIT Coursepack #2786 Gravimetric Analysis 96

 2. crystals begin as the infinitesimal nucleation site and grow to a colloid size

3. if colloid particles continue to grow, large crystals are then formed which do settle, can be
filtered and have low surface area resulting in much less impurities.

• after nucleation occurs, continued crystallization is a competition between forming new

nucleation sites and existing nucleation sites growing larger.

- for a given mass of precipitate, the more nucleation sites that are formed then the larger
the number of crystals there will be and consequently, the smaller the crystals will be ; these
crystals will be harder to filter and will have impurity problems because of the larger surface
area for impuritites to adsorb to: this is unwanted in a gravimetric analysis.

- for a given mass of precipitate, the fewer nucleation sites that are formed then the smaller
the number of crystals there will be and consequently the larger the crystals will be; these
crystals will be easier to filter and will not have impurity problems because of the smaller
surface area which does not adsorb impurities as much : this is desired in a gravimetric
analysis.

NAIT Coursepack #2786 Gravimetric Analysis 97

Summary:

add precipitating agent to analyte solution

saturated solution

supersaturated solution

initial nucleation producing

a few crystallization sites

continued crystallization

slow process fast process

existing nucleation sites more nucleation sites are

continue to grow created

results in few large crystals results in many small crystals

desired result / route undesired result / route

NAIT Coursepack #2786 Gravimetric Analysis 98

Homogeneous precipitation::

Ex: using thioacetamide to ppt Cu, Cd, Mo,& DMG for Ni. In these applications the pH of the
solution is adjusted slowly until precipitation occurs.

Heterogeneous precipitation: the precipitating agent is added slowly to the solution to initiate
precipitation on nucleation sites and continued until the analyte is fully precipitated.

Colloidal Precipitate

Description:

• occurs when the growth of the precipitating particle stops at the colloid stage.
• the colloid particles do not agglomerate/coagulate/combine into larger particles but they are
stabilized because of the surface charge they carry which repels the p article from each
other.

Example: precipitate Cl1– from NaCl solution with excess AgNO 3

NaCl (aq) + AgNO3 (aq) → AgCl  + NaNO3 (aq)

Limiting Reagent: these three species left after the reaction

• after the reaction, there is no Cl1– ion in solution and the excess Ag 1+ ion is common to the
AgCl precipitate.
• the Ag1+ ion will preferentially adsorb to the surface of the AgCl as a positively charged 1°
adsorbed layer.
• to balance the positively charged 1° layer, NO 31– ions will form a loosely adsorbed 2° or
counter-ion layer beyond this layer will be sodium ions. Note the excess silver ions
surrounding the solid particle.
Ag+ Positively charged
NO3- NO3- NO3-
- adsorption layer on
NO3 NO3- NO -
3 colloidal particle
NO3- Ag+ Ag+ H+
Ag +
NO3-
Cl- Ag+ Cl- Ag+ Cl- Ag+ NO3-
H+
Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ NO3-
NO3- Colloidal
-
NO3 Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ solid
+
H
NO3- NO3-
Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+
Ag+
Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ NO -
3 Counter-ion layer
+
H of solution with
NO3- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+
NO3 - excess anions
NO3-
Ag+ Ag+ Ag+
NO3-
NO3- - -
NO3 NO3 Ag +
H+
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NAIT Coursepack #2786 Gravimetric Analysis 99

 • the result is a positively charged particle surrounded by a large negatively charged layer
and the two layers together are referred to as the electrical double layer.
• when the negatively charged ionic atmosphere around the particle is very large, it prevents
two particles from approaching each other and possibly joining to form a larger particle; the
negative charge repels the particles.
• if particles cannot join together, then they will remain as a stabilized colloid.

How to overcome repulsive force and get particles to coalesce or join together:

Coagulation

• coagulated colloids are usually difficult to handle because they are not crystalline; they are
sticky and “curd” like with more coprecipitated impurities.
• there must be some electrolyte in the wash solvent when rinsing a coagulated colloid
precipitate, otherwise the solid will revert to colloid particles and rinse through the filter
paper.

Precipitation Equilibria

The solubility product is an expression of the equilibrium of the solubility of i norganic solids in
water.

The solubility product constant

Ksp:

NAIT Coursepack #2786 Gravimetric Analysis 100

for the sparingly soluble compound Ax By in water

Ax By (s) ⇋ x A(aq) + y B(aq)

Kc = [A]x [B]y
[Ax By (s)]

but [Ax By (s)] = 1

so Ksp = [A]x [B]y

Examples

PbCl2 ⇋ Pb2+ + 2 Cl1– Ksp =

Bi2S3 ⇋ Bi3+ + S2- Ksp =

Diverse ion effect

• a diverse ion is any ion which is not one of the ions in the solid ionic compound that is
dissolving.
• the effect is: as the concentration of the diverse ions increases, the solubility of the slightly
soluble compound increases (a screening effect on dissociated ions which leads to extra
dissociation)

• in the presence of diverse ions, the solubility product will increase.

Ex: as [KNO3] increases, the solubility of BaSO 4 increases.

the solubility (Ksp) is based on the dissolved ions in the water solution having water
molecules surrounding them; the ions are said to be “hydrated”
Ba2+(aq) is actually: Ba(H2O)62+(aq) and SO42+(aq) is actually: SO42–(H2O)n
if the hydration shell is replaced with some other species that makes the ion different than
the water hydrated ion., i.e. Ba(H 2O)62+(aq) is not the same as Ba(NO 3)64–

solubility equilibrium
BaSO4 (s) ⇋ Ba2+(aq) + SO42–(aq)
Competing equilibrium
Ba2+(aq) + NO31– ⇋ Ba(NO3)64-(aq)
As the concentration of NO 31– ion increases as KNO 3 is added, it will begin to
replace the water molecules surrounding the aqueous barium ion. The result is
the [Ba2+(aq)] goes down, the solubility equilibrium shifts right to replace Ba 2+(aq)
hence the more solid barium sulfate dissolves, i.e. increased solubility.
as the [KNO3] goes from 0 to 0.04 M, the solubility of BaSO 4 doubles.

NAIT Coursepack #2786 Gravimetric Analysis 101

Common ion effect

• the solubility of a slightly soluble ionic compound is an equilibrium process

• the equilibrium will shift to more ions dissolved, i.e. solid more soluble, when other solutes
in the solution compete for one of the dissolved ions in the equilibrium equation causing a
lower concentration of the dissolved ion.

Ax By (s) x A (aq) + y B (aq)

If [A (aq)] and/or [B (aq)]  then equilibrium shifts → meaning more solid dissolves.

• these effects are the opposite of the Diverse Ion Effect.

If one of the ions of a slightly soluble compound is added in excess of the normal saturation
amount, then the solubility of the compound is decreased; some compound will precipitate out of
solution.

It is expected that a decrease in solubility will occur with respect to Le Chatelier’s principle.

e.g. • soluble Ag NO 3 is added to a saturated solution of Ag 2CrO4.

• [Ag+1] goes up above the usual value according to the Ksp expression.
• for Ksp expression to be a constant, [CrO 4-2] must go down.

Effect of Complexation on solubility of slightly soluble ionic compound:

• this effect is the same idea as the pH equilibrium effect but the competing equilibrium
reaction is a non-acid/non-base equilibrium reaction.
• the reactive species is an ion or molecule which forms a “complex” with the dissolved metal
ion from the compound.

Solubility equilibrium
Al(OH)3 (s) ⇋ Al3+(aq) + 3 OH1–(aq)
Competing equilibrium
Al3+(aq) + F 1– ⇋ AlF 63–(aq)
(complex ion)
The fluoride ion reacts with the aqueous aluminum ion to for m a “complex” ion which
is very stable and soluble. As a result, the [Al+3] goes down and so the equilibrium
shifts to the right to replace the Al+3 ion causing more aluminum hydroxide solid to
dissolve → an increase in solubility.

• the AlF 63- complex ion effectively “masks” the aluminum from the solubility equilibrium
so the solubility equilibrium responds to a decrease the aluminum ion concentration.

Solubility equilibrium
AgCl (s) ⇋ Ag1+(aq) + Cl1–(aq)
Competing equilibrium
+ Cl1– (excess) ⇋ AgCl21–
(complex ion)
When precipitating AgCl in a gravimetric process, would use excess Cl 1– (from HCl)
to make sure of complete precipitation, i.e. common ion effect. However, to much
excess Cl1– causes the formation of a complex silver chloride ion and an increase in
solubility of the AgCl which would seriously affect the AgCl gravimetric mass.

NAIT Coursepack #2786 Gravimetric Analysis 102

Effect of pH on solubility of slightly soluble ionic compound:

• if one of the ions in a slightly soluble ionic compound can act as an acid or a base, then the
solubility of the compound depends on the pH of the solution.
• for BaSO4 the sulfate ion is a weak base and therefore will react with acids.
• adding hydrogen ions to the solubility equilibrium by lowering the pH, will cause the
concentration of the sulfate ion to decrease, so the equilibrium will shift to produce more
dissolved sulfate ions resulting in an increase in the amount of compound dissolving.

Solubility equilibrium
BaSO4 (s) ⇋ Ba2+(aq) + SO42–(aq)
Competing equilibrium
SO42–(aq) + H+ ⇋ HSO41–(aq)

Competing equilibrium reaction decreases the concentration of the

sulfate ion, so solubility equilibrium shifts right to increase sulfate
ion concentration resulting in more barium sulfate dissolving, i.e.
increase in solubility.

• solubility of BaSO4 increases if you add an acid which does not have a common ion with
the solid compound to an established solubility equilibrium
• adding HCl or HNO 3 would increase the solubility of BaSO 4

Effect of Temperature on the solubility of slightly soluble ionic compound

• usually, as temperature increases, the solubility increases.
• there are a few compounds which decrease their solubility with an increase in temperature.

KNO3
Solubility, g/100g

NaNO3
water

Na2SO4

Temperature, C
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Effect of Organic Solvents on the solubility of slightly soluble ionic compound:

NAIT Coursepack #2786 Gravimetric Analysis 103

Effect of Particle Size on the solubility of slightly soluble ionic compound

Improving Particle Size and Purity

Factors effecting purity

Co precipitation: soluble compounds are removed from solution in ppt formation

Co preciptitaion of a similar ion is referred to as mixed-crystal formation
Ex: when BaSO4 is ppt it can have SrSO 4 in the crystal.- main influence is from the sample
matrix- harder to fix (use diff ppt agent)

Surface adsorption issue in colloidal ppt but not with crystalline type- since adsorbed ions
(counterions in the secondary layer) are usually washed off. Can also improve by digestion.
Choice of wash (example washing with an acid to remove Cl ion allows the HCl which forms (its
volatile) to be removed in drying.

Occlusion: occurs as crystal rapidly grows and foreign ions get trapped in. entrapment occurs
when neighboring crystals grow together. Both at a min when ppt for mation rate is low (and
digestion improves)

Postprecipitation: As a precipitate stands (digests) impurities in the mother liquor may

precipitate on top of the product.

NAIT Coursepack #2786 Gravimetric Analysis 104

3. Isolation of Precipitate

Washing and Filtering

Washing can reduce contaminants that occur through coprecipitation and surface adsorption.
Caution needs to be taken when washing as peptization can occur. Peptization is the process of
reverting some of the precipitate back to the colloidal particle.
Ag2SO4(colloidal) Ag2SO4(s)
The reduction in particle size can result in loss of the precipitate. Ensuring the wash material is ice
cold can reduce the effect of peptization.

Drying or Igniting:

a. drying (low temperature) removes any solvent or volatile species by evaporation as in

NiDMG2 procedure; this is done in the 110°C oven.
b. ignition (strong heating) accomplishes two possible objectives:
ashing or decomposing organics, e.g. impurities, filter paper
Ex. the dry ashing of BaSO 4 in the lab; done in an 800°C furnace.
calculation: convert mass of precipitate to mass of analyte
Ex. g S / g BaSO4 ; g Ni / g NiDMG2

Thermal decomposition:

• convert precipitated compound into another compound with known, constant stoichiometry;
this requires high heat, i.e. 800°C
weigh to obtain an accurate mass.
CaC2O4·xH2O → CaO (+ CO  + CO2  + H2O  )
(variable molar mass) (constant molar mass)

4. Calculation of results from gravimetric data

Example:

A 0.500 g sample produced 0.250 g of BaSO 4. To determine the %w/w S we solve as:

NAIT Coursepack #2786 Gravimetric Analysis 105

9. Precipitation Titrations
• a titration analysis where the titration reaction produces a sparingly soluble compound as the
product, i.e. a product with a small Ksp value.
• the product appears as a precipitate in the titrate Erlenmeyer. The following are examples of
argentometric titration methods
• the Fajan or Mohr analysis for halide ion is an example of a precipitation titration where the
halide ion is titrated with silver ion producing an insoluble silver halide product :

Ag1+ + Cl1– → AgCl (s) Ksp = 1.82 × 10–10

Ag1+ + Br1– → AgBr (s) Ksp = 5.0 × 10 –13

Ag1+ + I1– → AgI (s) Ksp = 8.3 × 10 –17

• the Volhard analysis for thiocyanate ion is another example of a precipitation titration where
thiocyanate ion is titrated with silver ion producing insoluble silver thiocyanate:

Ag1+ + SCN1– → AgSCN (s) Ksp = 1.1 × 10 –12

• calculations for a titration curve require the concentration of the analyte in the titrate solution
but the analyte is also part of the precipitate, so the solubility K sp calculation and common ion
calculation are needed when constructing a titration curve ; for chloride analysis:

AgCl (s ⇋ Ag1+ + Cl1– and Ksp = [Ag1+] [Cl1–] = 1.82 × 10 –10

• when performing titration analyses match the analyte and titrant concentration so that a
reasonable titration volume is obtained, i.e. titrate 0.1 M analyte with 0.1 M titrant but titrate
0.01 M analyte with 0.01 M titrant.
• the precipitation reactions noted above have the required criteria for an acceptable titration
analysis reaction: quantitative, fast, constant and known stoichiometry, marked change at the
equivalence point.

NAIT Coursepack #2786 Precipitation Titrations 106

Titration Curve

• a titration curve is a graphical representation of the titration process

• a titration curve is the plot of the concentration of the analyte in logarithm form plotted against
the volume of titrant added.
• for the analysis of chloride ion by titrating with silver ion:

NaCl (aq) + AgNO3 (aq) → AgCl (s) + NaNO3 (aq)

Cl1–(aq) + Ag1+(aq) → AgCl (s)

(analyte) (titrant) (precipitate)

• the titration curve for this example would plot the chloride concentration as pCl versus volume
of AgNO3 added, where:
pCl = –1 × log [Cl1–] and [Cl1–] = molarity of Cl1–

• a sketch of a typical titration curve is shown below:

Titration Curve for 50.0 mL of 0.10 M NaCl

Titrated with 0.10 M AgNO3

9
8
7
6
equivalence
5 point
pCl

4
3
2
1
0
0 20 40 60 80
volume of AgNO3 added, mL

NAIT2014

Definitions for Regions in the Titration Curve

Region #1
• this point is the initial concentration of the analyte before any titrant is added and is calculated
from the molarity of the analyte as pCl = –1 × log[Cl1–]

Region #2
• this region is the partially titrated region where some of the analyte has reacted completely
with the added titrant but there is still some analyte remaining
• not enough titrant has been added yet: the titrant is the limiting reagent in the titration
reaction.
• in this region, the concentration of unreacted chloride analyte can be calculated as the initial
amount minus the amount reacted because the reacted amount has been removed from
solution as the precipitate.

NAIT Coursepack #2786 Precipitation Titrations 107

Region #3
• this is the equivalence point region where equal amounts of silver ion and chloride ion have
been combined with the result that all the chloride ion has been reacted and there is no silver
ion left in solution unreacted.
• the calculation of the chloride ion concentration in solution is a K sp calculation based on the
equilibrium solubility, i.e. what is the solubility of AgCl given the K sp value?

Region #4
• this is the over-titrated region where excess titrant has been added for the amount of analyte
present, so all the chloride ion has reacted and the amount of unreacted silver ion is
increasing
• the amount of chloride ion present in solution is a common ion calculation where there is a
saturated AgCl solution in the presence of excess silver ion

Limits of Analyte Concentration for Precipitation Titration

What effect does the concentration of the analyte have by a precipitation titration? Consider a
NaCl analyte where Cl1– is titrated with AgNO 3 ; use a 25.00 mL aliquot and match the Cl 1–
concentration with the AgNO 3 concentration

Conc of 0 mL AgNO3 24 ml AgNO3 25 m AgNO3 26 mL AgNO3 27 mL AgNO3

Cl1– pCl pCl pCl (eq pt) pCl pCl
0.10 M 1.00 2.69 4.87 7.03 7.32
0.01 M 2.00 3.69 4.87 6.03 6.32
0.001 M 3.00 4.57 4.87 5.03 5.32

Titration Curve for Various Concentations of Chloride

8
7
6
5
pCl 4
3
2
1
0
0 5 10 15 20 25 30
Volume of AgNO3 added, mL

0.10 M 0.01 M 0.001 M equivalence point

good poor no NAIT2014

General Conclusions:
The smaller concentrations do not give an adequate equivalence point region to allow a precise
indication of the endpoint with a visual indicator.

NAIT Coursepack #2786 Precipitation Titrations 108

Limits on Solubility, Ksp, of the Product in a Precipitation Titration

What effect does the solubility of the analysis reaction product have on the precipitation titration
process? Consider the titration of 25 mL of 0.10 M NaCl, 0.10 M NaBr and 0.10 M NaI titrated with
0.10 M AgNO3.

mL AgNO3 Added pCl pBr pI

(Ksp= 1.82 E-10) (Ksp= 5.0 E-13) (Ksp= 8.3 E-17)
0 1.00 1.00 1.00
25 (eq pt) 4.87 6.15 8.04
27 7.3 9.9 13.7

Titration Curve for Three Analytes

16

14

12

10
pAnalyte

0
0 5 10 15 20 25 30
volume of AgNO3

NaCl NaBr NaI

NAIT2014

General Conclusions:
By careful choice of an indicator there can be endpoint detection for these species, but for ions
which form precipitates with Ksp values much larger than about 10 -10 satisfactory end points are
not obtainable (ex Ksp(AgBrO 3) is ~10-5)

NAIT Coursepack #2786 Precipitation Titrations 109

Calculate the key points of a precipitation titration for the reaction of 50.00 mL of 0.10 M NaCl with
0.1 M AgNO3

1. Determine the equivalence point volume:

Ag1+ + Cl1- ⇌ AgCl(s)

2. Region #1-initial pCl

3. Region #2- partially titrated (pre-equivalence point)

This region is any volume from 0 mL up to but less than the equivalence point volume.

This calculation would be repeated at different volumes of silver nitrate added until the
equivalence point is reached.

NAIT Coursepack #2786 Precipitation Titrations 110

 Region #3-equivalence point

Region #4- over titrated (post equivalence point)

At all volumes past 50 mL of silver nitrate, the [Cl 1-] is found using the Ksp expression,
knowing the [Ag 1+].

Calculations such as these can be used to determine precipitation titration curves.

It can be seen in this titration curve that a large region exists in the equivalence point region to
determine a reasonably accurate endpoint with minimal titration error.

NAIT Coursepack #2786 Precipitation Titrations 111

Indicator Methods for Precipitation Titrations

General Requirements for an Indicator

• indicator should change very fast, i.e. the change should require very little titrant volume; this
produces precision for the titration volume
• the indicator change should be at or a small reproducible distance away from the equivalence
point; this produces accuracy for the titration volume
• in order for the indicator change to be fast and occur over a small volume of titrant, there must
be a physical property change at the equivalence point which is at least a factor of 100 in size,
i.e. 102 or 2 log units (2 “p” units)

Fajan Indicator Method

• used in the analysis of chloride ion with silver ion:

analysis reaction: NaCl (aq) + AgNO3 (aq) → AgCl (s) + NaNO3 (aq)
(analyte) (titrant) (precipitate)

• type of indicator is adsorption indicator

• indicator substance is dichlorofluoroscien, or DCF
Cl Cl Cl Cl

HO O OH HO O O

O -
O
C
O
O
DCF compound DCF 1– anion

• end point signal is the white AgCl precipitate turns a pink colour
• the colour change in the white precipitate occurs when the anion of DCF is adsorbed onto the
surface of the white AgCl precipitate where DCF 1– interacts with the solid to produce a pink
colour on the surface of the precipitate.
• the adsorption of the DCF 1– to the surface of the AgCl precipitate only occurs after the
equivalence point producing a positive titration error. The indicator adsorbs when the primary
adsorbed layer on the precipitate is the silver ion.

NAIT Coursepack #2786 Precipitation Titrations 112

Explanation of the Adsorption Indicator Action

Before the equivalence point:

• the titrate solution contains the unreacted analyte Cl 1– ion, all the added Ag 1+ ion has reacted
with the analyte and precipitated out of solution
• the Cl1– ion in the titrate solution is a common ion with the AgCl precipitate, so the Cl1– ion is
preferentially adsorbed to the surface of the AgCl precipitate as the primary adsorbed ion
layer; this is a negative ion layer
• the secondary adsorbed ion layer around the AgCl precipitate is positively charged containing
Na1+ ions to balance the negative primary adsorbed ion layer
• the DCF 1– indicator ion is not attracted by the negatively charged primary layer, so there is no
indicator action before the equivalence point

At the equivalence point:

• there are no Cl1– ions nor Ag1+ ions remaining in the titrate solution now
• there are no common ions to the AgCl precipitate so there are no definite adsorbed ion layers
around the precipitate
• the DCF 1– ion is not attracted to the precipitate surface, so there is no indicator action at the
equivalence point

After the equivalence point:

• the titrate solution now has no Cl 1– ion left in solution; it is totally reacted
• the titrate solution contains excess Ag 1+ ions, common to the AgCl precipitate
• the primary adsorbed ion layer is now the Ag1+ ion making this layer a positive charged ion
layer
• the secondary ion layer will contain negatively charged ions to balance the positively charged
primary ion layer
• the secondary ion layer will contain NO 31– ions and some DCF 1– indicator ions.
• when the DCF 1– indicator ions become adsorbed in the secondary layer of the AgCl
precipitate, the colour of the surface of the precipitate changes from white to pink; this colour
change is the indicator action which signals the end point has been reache d and to stop
titrating

NAIT Coursepack #2786 Precipitation Titrations 113

Adsorption Indicator depends on the following for a sharp, fast action:

1. requires a very fine (colloidal) precipitate particle

• fine particles ensure that there is a very large surface area available so that lots of DCF 1–
ions are adsorbed to the secondary ion layer quickly
• fine particles are produced in the lab by fast addition of the AgCl and rapid stirring to
promote fast precipitation and dextrin is added to the titrate solution to prevent the
precipitate particles from combining to produce larger particles

2. requires a sudden change at the equivalence point to trigger the indicator action
• need a sudden Ag 1+ concentration to establish the positive primary ion layer so that the
DCF 1– ion can be attracted into the secondary ion layer
• this aspect depends on the concentration of Ag 1+ ion and the Ksp of the precipitate

3. requires pH control
• use an acetic acid/sodium acetate buffer in the titrate solution for a pH~4.8 so that there is
a sufficient supply of the DCF 1– anion form of the indicator

4. requires constant stirring/swirling

• this keeps the precipitate solid suspended so that the change to a pink coloured surface
can be seen easily and quickly

Errors Associated with an Adsorption Indicator

• the problem is the indicator action occurs after the equivalence point, giving a positive titration
error, i.e. over-titration
• running a blank can be used to measure how much over-titration occurs and a correction could
be applied, however, in these systems a blank cannot be made that produces reliable results
• the correction is to run the standardization and the analysis titration exactly the same way; in
this way, the titration error is the same in both procedures and so it should be minimized

NAIT Coursepack #2786 Precipitation Titrations 114

Volhard Indicator Method

• used in the analysis of Ag 1+ ion with standardized thiocyanate ion, SCN 1–:

analysis reaction: Ag1+(aq) + SCN1–(aq) → AgSCN (s)

(analyte) (titrant) (precipitate)

• the indicator type is a soluble complex ion indicator

• the indicator substance is the iron (III) ion, Fe 3+, as supplied from ferric ammonium sulfate,
FeNH4(SO4)2
• the indicator reaction is:

SCN1–(aq) + Fe3+(aq) → FeSCN2+(aq)

(excess titrant) (indicator, yellowish) (red solution)

• indicator compound is yellow but the concentration is very low so the yellow colour is very faint
and does not interfere
• the indicator reaction does not occur when there is Ag 1+ ion available since the SCN1– ion
preferentially reacts with the silver ion
• the indicator reaction occurs when all the Ag 1+ ion is gone and there is a slight excess of
SCN1– ion added, i.e. occurs after the equivalence point, over -titrated
• the end point signal is the solution turns red because the red coloured FeSCN 2+ ion is in the
solution
• the end point signal is somewhat difficult to see because there is also the white AgSCN
precipitate in the titrate obscuring the red colour of the solution
• an advantage of the Volhard method is ions such as CO 32–, C2O42– and AsO43– that may be in
the analyte solution will stay in solution and not interfere with the analysis because the titrate
solution is made quite acidic with the addition of nitric acid

Errors Associated with the Volhard Indicator Method

• a blank cannot be used to correct for the required over-titration to cause the indicator action,
so the standardization and analysis must be done exactly the same so the over -titration error
cancels
• when the Volhard indicator method is used in a back titration process to determine the amount
of Cl1– ion then there are two precipitates present in the titrate, AgCl (s) and AgSCN(s);
because the silver thiocyanate is less soluble than the silver chloride, the silver chloride goes
back into solution and reacts with the SCN 1– titrant causing an over-titration error, so the AgCl
must be removed by either filtering off or masked by coating with an insoluble organic
compound such as nitrobenzene

This type of titration (determination of a halide by adding excess Ag 1+ and titrating with SCN1-) is
referred to as a back titration. The amount of Ag 1+ added minus what reacts with SCN 1- equals the
amount of Ag 1+ that reacts with the halide.

If 50.00 mL of 0.100 M AgNO 3 is added to a 0.6500 g sample of a chloride salt and the excess Ag +
is titrated with 22.50 mL of 0.1106 M KSCN. Determine the %Cl in the sample. (13.70%Cl)

AgNO3 + Cl1- → AgCl + NO31- and Ag1+ + SCN1- → AgSCN

NAIT Coursepack #2786 Precipitation Titrations 115

Mohr Indicator Method

• used for the direct analysis of Cl1– ion by titration with Ag 1+ion (same as Fajan)

Ag1+(aq) + Cl1–(aq) → AgCl(s)

• indicator type is a secondary precipitate indicator because there are two precipitates produced
in this method, AgCl and Ag 2CrO4

• indicator compound is sodium chromate, Na 2CrO4

• indicator reaction:
2 Ag1+(aq) + CrO42–(aq) → Ag2CrO4 (s)
(excess titrant) (indicator ion, yellow) (red precipitate)

• the end point occurs when the second red precipitate appears in the titrate along with the
white AgCl precipitate which will appear as a pink precipitate; keep swirling to suspend the
precipitates so you can see the colour
• the indicator reaction occurs only when there is excess Ag 1+ ion titrant present, i.e. over-
titrated, so run the standardization and the analysis exactly the same so the positive titration
error will cancel

NAIT Coursepack #2786 Precipitation Titrations 116

11. Determining Analytical Errors
Errors in Sampling
• field sampling error is difficult to quantify

• lab sampling error can be defined mathematically

• total error of the analytical method is determined as

• smethod can be improved via improving either s sampling or/and sanalysis, for that we need to know
which error has the most contributing factor
• sanalysis is determinate error, while ssampling is mostly indeterminate error; it’s easier to
decrease sanalysis
• If ssampling  3x sanalysis , decreasing sanalysis will have insignificant effect on s total
• To determine which step (sampling or analysis) has the greatest effect on the overall
method error (smethod), we need to measure both s sampling and sanalysis

NAIT Coursepack #2786 Determining Analytical Errors 117

Sample size

• To minimize sampling errors, sample must be of an appropriate size.

• If a sample is too small, its composition may differ substantially from that of the site of interest,
introducing a sampling error.
• Samples that are too large require more time and money to collect and analyze, without
providing a significant improvement in the sampling error
• It is advisable to calculate the mass of a representative sample using Ingamell’s equation

Errors in analysis

The following method is used for "one time" circumstances where no historical data is available.
Analytical results are typically accompanied by an indication of the error associated with the
method. This includes but is not limited to the errors from:

stock: weighing / balance

glassware
standards: glassware – volumetric flasks and pipettes (use the solution that produces
the highest error
unknown: weighing / balance
glassware – volumetric flasks and pipettes (all)
instrument

The error is indicated as either a relative or absolute error of the result. Relative error is reported
as the total percent error (± %) and the absolute error is calculated from the relative error and is
reported in the same units as the measurement.

A spectrophotometric analysis of cobalt is performed from a sulfide ore sample using the following
procedure (condensed):
1. 0.4689 g of dried CoCl2 was weighed and diluted to 250.00mL in a volumetric flask.
2. Five (5) standard solutions were prepared by pipetting 1.00 mL, 2.00 mL, 5.00 mL, 8.00 mL
and 10.00 mL into 100.00 mL individual volumetric flasks.
3. The absorbance of the standards were measured at 380 nm.
4. 0.9547 g of a dried unknown ore sample was weighed. The sample was digested and
transferred to a 250.00 mL volumetric flask.
5. Three replicate samples were prepared by pipetting 5.00 mL into 100 mL volumetric flasks.
6. The absorbance of the replicates was measured at 380 nm.

A standard curve of absorbance vs concentration of Co (ppm) was prepared and produced a

line equation of y = 0.01176 x + 0.0006. The average absorbance of the unknown replicates
was 0.489.

NAIT Coursepack #2786 Determining Analytical Errors 118

Calculate the mass of Co (mg) in the unknown ore.

Solution Preparation Error Calculation

1. Error from stock solution = weighing error + 250 mL volumetric flask

2. Preparation of standards

3. Unknown solution

4. Instrument error =

NAIT Coursepack #2786 Determining Analytical Errors 119

 5. Total error = 1+2+3+4 =

Result, with relative error ±

Result, with absolute error ±

NAIT Coursepack #2786 Determining Analytical Errors 120

Interpretation of Analytical Results:
(precision / accuracy / reliable / acceptability)

1. Collection of analytical data

Calibration curve:
Set of standards of concentrations that bracket the concentrations of the check standard
and unknown.
Ideally a linear relationship. Determine and display line equation and R 2.

R2 of calibration curve indicates precision (the linearity of the calibration = how confident the
extrapolation of data from the graph)

Check standard (control sample):

Indication of the accuracy of the method – how reliable the results of the measured samples
are. Accuracy or reliability is assessed by comparing %deviation for the check std to the
%REtotal check std
Allows to determine whether the calibration is accurate (how close the experimental value is
to the true value).
If the measured value (unknown) is below the lowest calibration standard, the value still
should be reliable especially if the method accuracy is confirmed by the check standard

Unknown sample (analytical sample):

Report value with the proper units and significant figures
Ensure the result is within the appropriate analytical range:
For single point = within 0.5x to 1.5x calibration standard (also applies to standard
addition)
For multi-point = value bracketed by calibration standard

To provide complete assessment of the unknown determine the %REtotal unk .

2. Interpretation (see flowchart)

a. evaluate graph precision using R2

Four “9s” or more = Excellent
Three “9s” or more = Good
Two “9s” or more = Satisfactory
One “9” or more = Poor – recalibrate, little to no confidence in data extrapolated

b. evaluate accuracy from the check standard data

Calculate % deviation and %REtotal check std

If % deviation  %REtotal check std, then results for the check std are accurate = can trust
the unknown value
If % deviation > %REtotal check std, the results for the check std are NOT accurate =
unknown results are questionable

NAIT Coursepack #2786 Determining Analytical Errors 121

 c. evaluate accuracy and precision of the unknown

Calculate %RSD and %REtotal unk for the unknown

Base evaluation on how and/or what type of unknown samples are analyzed as triplicates

i. single unknown is run 3 times = compare %RSD to %instrument error

If %RSD  %instrument error = results are within the experimental error – results may
be precise but may not be reliable (inaccurate)
If %RSD > %instrument error = the replicate analysis are outside the instrument error –
not precise and not reliable (accurate)

Further evaluation may be required if the %RSD > %REtotal unk

ii. multiple samples independently prepared are analyzed

If %RSD  %REtotal unk = unknown data is reliable
If %RSD > %REtotal unk = the unknown data is unreliable

NAIT Coursepack #2786 Determining Analytical Errors 122

Interpretation of Analytical Results

Prepare standards, check standard and

unknown samples

Instrument
Measure standards Measure check standard

Calibration Curve Calculate using line equation

Report with correct significant figures and
units

Calculate %RSD

Calculate
2 %REtotal check std
Line Equation R:
- linearity of
calibration Calculate % deviation
- precision - compare % deviation to %RE total check std
If:
Conf idence in the extrapolated of % deviation  %REtotal check std, then results for the check
data f rom the graph: std are accurate = we can trust the unknown value
Four “9s” or more = Excellent
Three “9s” or more = Good
% deviation > %REtotal check std, the results for the check
Two “9s” or more = Satisfactory std are NOT accurate = unknown results are
One “9” or less = Poor questionable

Measure unknown

One sample three Three

measurements samples

Calculate using line equation

Report with correct significant figures and units

Calculate %RSD Calculate %RSD

Calculate Calculate
%REtotal unknown %REtotal unknown

%RSD to %REtotal unk %RSD to %REtotal unk

If: If:
%RSD  %instrument error = results are within the %RSD  %REtotal unk = unknown data is reliable
experimental error – results may be precise but %RSD > %REtotal unk = the unknown data is
may not be reliable (inaccurate) unreliable
%RSD > %instrument error = the results are
outside the experimental error – not precise and
not reliable (accurate)

NAIT Coursepack #2786 Determining Analytical Errors 123

11. Spectroscopy
Spectrometric methods: science that deals with the interaction of electromagnetic radiation or emr
(forms of energy) and matter; measure the intensity of radiation with an electronic device.
The interaction tells us the different molecules or atoms present in the material and their quantities.
Use of light allows us to study the composition and structure of matter.
Spectroscopy: http://www.spectroscopymag.com

Operations performed by an instrument

Optical spectroscopic methods are based on absorption, fluorescence, phosphorescence,

scattering, emission, and chemiluminescence.

Instrument components

Instruments used to measure changes in the above process have some fundamental designs.
Instrument converts some process to an interpretable signal.

The following set of instrument orientations illustrates the way in which different spectro scopic
methods could be set up. Typically five components are required

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NAIT Coursepack #2786 Spectroscopy 124

Interaction of emr with matter

• Reflection:

• polarization:

• optical rotation:

• refraction: the bending of a beam of light as it passes obliquely from one medium into another
of different density.

• diffraction: the bending of light as it passes close to a sharply defined edge

• dispersion: is the separation of wavelengths (as a result of refraction or/and diffraction)

Contrast diffusion.

• transmission: the light passes through the matter with no apparent change occurring

• scattering: the small fraction of light which is transmitted in all directions from the original path.
Amount scattered increases with particle size.

The above definitions illustrate the wave nature of light. To best explain the transfer of energy,
which occurs with interaction, it is best to think of light as discrete p articles called photons or
quanta.

• absorption: some of the light is absorbed; i.e., some energy from the emr is transferred to the
electrons of the matter (in UV-Vis region)

• Fluorescence: radiant emission of energy occurs after excitation occurs. The e mitted energy is
usually less than the excitation (absorbed) energy. Process is slower than emission.

• Phosphorescence: molecule relaxes to some metastable excited state prior to emission of

energy. Can have very long lifetimes (>10 -5 seconds)

• Emission:

NAIT Coursepack #2786 Spectroscopy 125

Regions of the emr spectrum, the type of quantum transition, and the type of spectroscopy
employed.

Emr region λ range Type of transition Type of spectroscopy

X-ray 0.1-100 A Inner electron X-ray absorption,
emission,
fluorescence, and
diffraction
UV 10-400 nm Bonding electrons UV absorption
Visible 400-700 nm Bonding electrons Visible absorption,
emission,
fluorescence
Infrared 0.78-300µm Rotation and Infrared absorption
vibration
Microwave 0.75-3.75 mm Rotation of Microwave absorption
molecules
Radio 0.6-10 m Nuclear spin in Nuclear magnetic
magnetic fields resonance
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Since energy absorption is quantized (see photoelectric effect), there must be an energy
match. To cause the particular transition the energy must match the energy of the transition.
i.e., for neutral sodium atoms to absorb at 589.59nm and 590.00nm, (light with) those
identical energies must be available to the 3s electrons

Spectral Appearance; Atoms, ions and molecules have discrete energy states and can absorb or
emit energy exactly equal to the energy difference between these states. The energy absorbed or
emitted is related to the frequency of radiation by ΔE=h, and ΔE is E1-E0. E1 is the higher
electronic state and E0 is the lower electronic state. This can be seen in the following diagram:

E*
1
+ hv fast
that matches relaxation + hv

0
E

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Normally, the processes’ lower state (E0) is the lowest energy state (the ground state).

The observed spectra we would get for an atom is called a line spectra, since the energy level
diagram for an atom consists of discrete electronic energy levels.

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Molecules are more complex, since they have vibrational and rotational levels within the electronic
energy levels. As a result we observe band spectra:

NAIT Coursepack #2786 Spectroscopy 126

The spectrum of the permanganate ion
E = Eelectronic + Evibrational + Erotational

Spectral Absorbance Curve for Permanganate  max

A
B
S
O
R
B
A
N
C
E
300 350 400 450 500 550 600 650 NAIT2014
Wavelength (nm)

• for a molecular species the real picture has interaction with the solvent in the solution
(absorption lines broaden extensively with molecular interaction with the solvent It can be
seen in the above diagram that the greatest interaction with light occurs at 525 nm. The
degree of interaction is given by absorptivity. There is a greate r absorptivity at 525 nm than at
545 nm.

The line-blending effect in molecular spectra is due to the interaction of the electrons of the
molecule with other electrons of the molecule (when PURE) and/or with electrons of the solvent
molecules(when in SOLUTION)

Lambda-max (max)
Epsilon

Define Beers-Lambert law and do calculations using it.

Beer's Law
Absorbance(A) = Epsilon() x Pathlength(b) x Concentration(C)

A=xbxC or A=axbxc

Where:

NAIT Coursepack #2786 Spectroscopy 127

Example 1: if = 4200L/mole-cm, b = 20mm, and C = 1 x 10 -4mole/L

Example 2: if c = 31mg/L

From Ex 1 and Ex 2:What is the molar mass in grams?

While A depends on both b and C (or c), the pathlength is usually kept constant and A is then
proportional to C (or c).

If a 0.0010 M solution gave an A= 1.00 in a 1.00 cm cell, what would ε be? What would ε be in
2.00 cm cell?

NAIT Coursepack #2786 Spectroscopy 128

Limitations to Beer's Law

a) Real limitation: Intended for dilute solutions

b) Association or dissociation of species...

i.e., Cr 2O72- + HOH ⇋ 2CrO42- + 2H+

λmax = 350nm λmax = 372nm

If you dissolve a dichromate in distilled water and take the Absorbance values at 350nm, they will
be low because some of the dichromate converts to chromate
. . 2- + H O  2 H + + O4 2-
2 O7 2

 x = 360 & 400  x = 380

T ft , [ 2-]
2 O7 , vs v .

c) Refractive index and stray radiation

At low [ ] the refractive index, , of the solution is close to or essentially the  of the solvent. As [ ]
increases above 0.01 M,  changes. This can cause the light beam to change its focus on the
detector.

At low [ ]

light source samplecell detector

At moderate to low [ ]

 changes

Stray radiation (radiation reaching the detector not absorbed by the sample (quality of
instrument) gives low A values

NAIT Coursepack #2786 Spectroscopy 129

d) Monochromatic light is required

I II

A A

C C NAIT2014

In case #I: the range of wavelengths supplied by the instrument is narrow compared to the
width of the compound absorbance band

Thus A will be essentially as high as though only a single wavelength were supplied at max

In case #II: the range of wavelengths supplied by the instrument is wide compared to the width
of the compound absorbance band

Thus A will be low compared to the value obtained with a single wavelength supplied at max

NAIT Coursepack #2786 Spectroscopy 130

Quantitative Evaluation

use calibration curves, standard addition, internal standards (rarely in uv-vis).

a) Standard graph (calibration curve)

Advantage of standard graphs is one can do lots of samples against the curve. Best statistical
comparison is in the middle 2/3 of the analytical curve. This may require sample dilution.
Samples must be reasonably "clean" –not have a complex matrix
Standards should approximate the sample matrix if possible.

• Concentration can be
Calibration curve obtained by:

1 • read the concentration

Absorbance = 0.0205 * concentration - 0.006 on the x –axis at the
0.8 point that the
R2 = 0.9994
absorbance reading
Absorbance

0.6 intersects the

Absorbance of sample regression line.
0.4
• calculate the
0.2 Concentration of sample concentration
0 according to x = (y-
b)/m
0 10 20 30 40 50
-0.2
• the wavelength chosen
Concentration (mg/L) should provide a large
 to enhance
sensitivity
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The equation for the line in this example is y = 0.0205x +-0.006. The sample gives an A = 0.32.
The sample concentration is:

If the sample was taken from a solution using a 10.0 mL aliquot and diluting to 100.0 mL then the
concentration of the solution is 160 mg/L.

NAIT Coursepack #2786 Spectroscopy 131

b) Standard-Addition:

Start STD’s (with chemical reagent), add fixed amount of unknown to each STD (referred to as
spiking)
Dilute, mix, and read %T (A) then plot A vs. C of std (added)

To evaluate unknown

Very time-consuming because only one value for one unknown per one graph

The Co in an aqueous solution was determined by pipetting 10.0 mL of unknown into four separate
50.0 mL flasks. Various volumes of a 6.23 ppm Co standard were added. The flasks were diluted
to volume and the following results were obtained.

Solution Volume of Volume of Concentration Absorbance

unknown, standard of Co added, at 625 nm
mL added, mL ppm
1 10 0 0.159

2 10 10 0.250
3 10 20 0.336

4 10 30 0.425
5 10 40 0.512

One can plot Absorbance vs volume added or Absorbance vs. Concentration added. Verify that
the 10 mL vol added is 1.246 ppm.

Standard Addition Method (2) Standard addition method

0.6
0.6 0.5
Absorbance

0.5
Absorbance

0.4
0.4
0.3 0.3
0.2 0.2
0.1
0.1
0
-4 -2 -0.1 0 2 4 6 0
-20 0 20 40 60
Concentration of Standard (ppm)
Volume of standard (mL)
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NAIT Coursepack #2786 Spectroscopy 132

c) Single Standard-Addition

Recovery
Definition:

An analyte spike is a known level of analyte or surrogate added to a matrix similar to that of the
sample before or during processing. The recovery of this spike in the final sample analysis is a
measure of analyte loss through the sample preparation process.

The recovery is calculated by:

[𝑥 𝑠𝑝𝑖𝑘𝑒𝑑 ] − [𝑥 𝑢𝑛𝑠𝑝𝑖𝑘𝑒𝑑 ]
%𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = 𝑥100
𝐶𝑎𝑑𝑑𝑒𝑑

Where xspiked = mean concentration of spiked samples

Xunspiked = mean concentration of unspiked samples
Cadded = concentration of analyte added
Since the concentration which are determined are directly related to the measured value (for
example A), this can be expressed as:

𝐴𝑠𝑝𝑖𝑘𝑒𝑑 − 𝐴𝑢𝑛𝑠𝑝𝑖𝑘𝑒𝑑
%𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = × 100
𝐴𝑠𝑝𝑖𝑘𝑒

Sample problem: an sample solution gives a signal of A=0.100, a 1.00% standard gives a
signal of A= 0.120, a new solution which has sample and 1.00% standard gives a signal of
0.210. What is the %recovery?

0.210− 0.100
%𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = × 100 = 91.7%
0.120

Need two solutions for each sample:

A sample to give AS and a Sample + STD to give AS+STD, then
AS+STD/CS+STD = AS/CS

Ex 1. Suppose that AS = 0.176, AS+STD = 0.382, CSTD = 3.38ppm, then

NAIT Coursepack #2786 Spectroscopy 133

Solve the problem when 5.12 g sample is diluted to 200 mL, then two 50 mL aliquots taken, to the
second one 4 mL of 3.82 ppm Cu added. Both diluted to 100 mL. Note the dilution of the
standard. Determine %Cu. Use the Absorbance values in Ex 1.

UV-Vis Spectrophotometry as a Quantitative tool

Procedural details:

UV-Vis Spectrophotometry as a Qualitative tool

UV-Vis can indicate the presence or absence of unsaturation

UV spectrum is usually reasonably detailed, can give some info as to possible functional groups.
Visible spectrum is usually unremarkable and thus of little use for qualitative work.

Useful aspects are:

• with other physical and chemical tests, it can help in identification
• if a good match of a spectrum of A vs  is obtained, it can be used for a tentative
identification.
• Instruments which use UV detectors are looking only for functionality. (non -specific detectors)
• Instruments that can scan the UV region usually look at ratios of molar absorptivities at some
wavelengths. Agreement among scans is useful for identification and purity.

NAIT Coursepack #2786 Spectroscopy 134

Colored complexes in analytical chemistry

A chromogen is a type of chromophore which, typically, produces a colored product; it is often used
when the analyte (ion) is a poor absorber such as Cu 2+(pale blue), Fe 3+(yellow-brown), or Fe 2+(pale
green). These elements have d electrons which can be excited by emr. The d orbitals are
considered to be degenerate until they are influenced by ligands.

The stronger a ligand is the more it increase the energy required for an electronic transition from
d-d*.

 oct is the energy difference between levels. Ligands ordered in the spectrochemical series of
ligands are arranged in the order in which they split the field.

Look up the spectrochemical series and place the ligands chloride water thiocyanate and o phn in
order of increasing ligand field strength.

If the ligands can participate in an internal redox reaction with the metal ion like SCN -1 and o-phn
then the molar absorptivity increases immensely.

The basic idea is as follows:

Analyte ε (L/mole-cm) Chromogen Product ε (L/mole-cm)

Cu2+ 15 NH3(aq) Cu(NH3)42+ 60
Fe3+ 5 SCN1- Fe(SCN) n(3-n)+ 9000
Fe2+ 2 o-phn Fe(o-phn)32+ 13000

For the chromogen, the most desirable property is specificity; there are other useful attributes
such as low cost, good solubility, good stability in solution, etc.,

For the colored product, desirable properties are

A sample has a Fe3+ concentration of 0.000010 M. If it is analyzed in a 1.0 cm cell at its λmax what
would the absorbance be? What would you do to increase the absorbance to a more realistic
value (eg. ~ 0.5 A)?

NAIT Coursepack #2786 Spectroscopy 135

 Appendix

NAIT Coursepack #2786 Appendix

Common Indicators
Transition High pH
Indicator Low pH color
pH range color
blue-
Gentian violet (Methyl violet 10B) yellow 0.0–2.0
violet
Leucomalachite green (first transition) yellow 0.0–2.0 green
Leucomalachite green (second
green 11.6–14 colorless
transition)
Thymol blue (first transition) red 1.2–2.8 yellow
Thymol blue (second transition) yellow 8.0–9.6 blue
Methyl yellow red 2.9–4.0 yellow
Bromophenol blue yellow 3.0–4.6 purple
Congo red blue-violet 3.0–5.0 red
Methyl orange red 3.1–4.4 yellow
Bromocresol green yellow 3.8–5.4 blue
Methyl red red 4.4–6.2 yellow
Methyl red red 4.5–5.2 green
Azolitmin red 4.5–8.3 blue
Bromocresol purple yellow 5.2–6.8 purple
Bromothymol blue yellow 6.0–7.6 blue
Phenol red yellow 6.4–8.0 red
Neutral red red 6.8–8.0 yellow
colorless to greenish
Naphtholphthalein 7.3–8.7
reddish to blue
reddish-
Cresol Red yellow 7.2–8.8
purple
Phenolphthalein colorless 8.3–10.0 fuchsia
Thymolphthalein colorless 9.3–10.5 blue
Alizarine Yellow R yellow 10.2–12.0 red
http://en.wikipedia.org/wiki/PH_indicator

NAIT Coursepack #2786 Appendix

Ionization Constants of Aqueous Monoprotic Acids
Common Name Formula Constant pKa
acetic acid CH3COOH 1.76 x 10-5 4.754
benzoic acid C6H5COOH 6.31 x 10-5 4.200
chloroacetic acid CH2CICOOH 1.36 x 10-3 2.866
cyanic acid HOCN 3.54 x 10-4 3.451
dichloroacetic acid CHC12COOH 5.68 x 10-2 1.246
ethanol CH3CH2OH 1.31 x 10-14 13.882
formic acid HCOOH 1.86 x 10-4 3.732
hydrochloric acid HCl greater than 1 negative
hydrocyanic acid HCN 5.85 x 10-10 9.233
hydrofluoric acid HF 6.94 x 10-4 3.159
hypochlorous acid HC1O 2.81 x 10-8 7.551
lactic acid H3CCH(OH)COOH 1.37 x 10-4 3.863
nitric acid HNO 3 greater than 1 negative
nitrous acid HNO 2 5.98 x 10-4 3.224
perchloric acid HC1O 4 greater than 1 negative
phenol C6H5OH 1.08 x 10-10 9.968
water H2O 1.0 x 10-14 14.0

Ionization Constants of Aqueous Weak Bases

Common Name Formula Constant pKb

ammonia NH3 1.80 x 10-5 4.745
aniline C6H5NH2 3.94 x 10-10 9.405
dimethylamine (H3C) 2NH 5.49 x 10-4 3.261
imidazole C3H3NNH 9.80 x 10-8 7.008
methylamine H3CNH2 4.18 x 10-4 3.378
trimethylamine (H3C) 3N 5.81 x 10-5 4.237
pyridine C5H5N 1.47 x 10-9 8.833

Ionization Constants of Aqueous Polyprotic Acids

Common Name Formula Constant pKa

boric acid H3BO 3 K1 = 5.78 x 10-10 9.238
carbonic acid H2CO 3 K1 = 4.35 x 10-7 6.361
HCO 3- K2 = 4.69 x 10-11 10.329
chromic acid H2CrO 4 K1 = greater than 1 negative
HCrO 4- K2 = 3.36 x 10-7 6.473
citric acid HOC(CH2COOH) 3 K1 = 7.42 x 10-4 3.130
K2 = 1.75 x 10-5 4.757
K3 = 3.99 x 10-6 5.602
EDTA C2H4N2(CH2COOH) 4 K1 = 9.81 x 10-3 2.008
K2 = 2.08 x 10-3 2.683
K3 = 7.98 x 10-7 6.098
K4 = 6.60 x 10-11 10.181
hydrogen sulfide H2S K1 = 1.02 x 10-7 6.992
HS- K2 = 1.22 x 10-13 12.915
oxalic acid HOOCCOOH K1 = 5.40 x 10-2 1.268
HOOCCOO - K2 = 5.23 x 10-5 4.282
phthalic acid C6H4(COOH) 2 K1 = 1.13 x 10-3 2.946
K2 = 3.90 x 10-6 5.409
phosphoric acid H3PO 4 K1 = 7.11 x 10-3 2.148
H2PO 4- K2 = 6.23 x 10-8 7.206
HPO 42- K3 = 4.55 x 10-13 12.342
succinic acid C(CH2) 2COOH K1 = 6.21 x 10-5 4.207
HOOC(CH2) 2COO - K2 = 2.31 x 10-6 5.636
sulfuric acid H2SO 4 K1 = greater than 1 negative
HSO 4- K2 = 1.01 x 10-2 1.994
sulfurous acid H2SO 3 K1 = 1.71 x 10-2 1.766
HSO 3- K2 = 5.98 x 10-8 7.223
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NAIT Coursepack #2786 Appendix

 Tolerances of Standard Laboratory Glassware and Equipment

Glassware Item Capacity (mL) Tolerance (±mL) %Error

Volumetric Pipets 1 0.006 0.600
2 0.006 0.300
3 0.007 0.233
4 0.009 0.225
5 0.010 0.200
10 0.015 0.150
20 0.020 0.100
25 0.025 0.100
50 0.035 0.070
100 0.050 0.050
Measuring Pipets 1 0.010 See Note
2 0.010
5 0.020
10 0.030
25 0.050
Volumetric Flasks 10 0.008 0.080
25 0.015 0.060
50 0.030 0.060
100 0.050 0.050
250 0.110 0.044
500 0.140 0.028
1000 0.190 0.019
Graduated 5 0.03 See Note
Cylinders 10 0.03
25 0.17
100 0.25
Buret 50 0.04 See Note
Weighing Error ±0.3 mg
Micropipet (min) 0.1 0.002 2.0
0.2 0.002 1.0
0.5 0.004 0.8
(max) 1.0 0.006 0.6

Note: The use of a graduated cylinder, a measuring pipet, or buret, to measure less
than its nominal capacity does not change the assigned tolerance; it does, however,
increase the percentage of the calculated error.

Instrumental Error for a Spectrophotometer

Instrument Error
SPECTRONIC 21 ± 0.15 %T
D.B. SPECTROPHOTOMETERS ± 0.003 A at 1.00 A
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NAIT Coursepack #2786 Appendix

References:

1. Gilreath, Elementary Quantitative Chemistry, W. H. Freeman and Company, 1969, p 3

2. Skoog, West, Holler and Crouch, Analytical Chemistry, An Introduction, Saunders College
Publishing, 7 th Edition, 2000, p. 4, 6

3. Taylor, J. K., Quality Assurance of Chemical Measurements, Lewis Publishers, Inc, 1987

4. Mattj63 (2007), Detection Limit, Retrieved from http://en.wikipedia.org/wiki/File:LOD.png

5. pH indicator, Retrieved from http://en.wikipedia.org/wiki/PH_indicator

6. Pearson Education On-Line resources, Acid-Base Titrations,

http://wps.prenhall.com/wps/media/objects/3083/3157555/blb1703.html

7. Gutz, I. G. R. (2014), Acid Base Titration Plot,

http://www2.iq.usp.br/docente/gutz/Curtipot_.html

8. Cheng, W. (1998), DCI, Concentration, Acidity and Neutralization, www.rejuvilab.com/ph.pdf

9. ChemBuddy (2009), Potentiometric titration, http://www.titrations.info/potentiometric-titration-

curve-calculation

10. E. Generalic, http://glossary.periodni.com/glossary.php?en=calomel+electrode

11. Kaverin (2010), Glass Electrode Scheme,

http://en.wikipedia.org/wiki/File:Glass_electrode_scheme-1.jpg

12. www.acdlabs.com

13. Petergans (2011), Schematic of Gouy Balance, http://en.wikipedia.org/wiki/File:Gouy_bal.png

14. Christian, Gary, Analytical Chemistry, John Wiley & Sons, 6 th Edition, 2004

15. CALA Guidance on Traceablility (2012), http://www.cala.ca/A61-02-

Guidance_on_Traceability.pdf

NAIT Coursepack #2786 References