Second Year Analytical Chemistry

WSU in October 2018

Please remind me to explain these notes to you before
Test 2 on Monday 29 October 2018!

CHE21M2 topics include:

Statistics and Chemometrics for Analytical Chemists

Classical Methods of Analysis
Gravimetric Methods of Analysis.
Titrimetric Methods of Analysis:
Precipitation Titrimetry.
Principles of Neutralization Titrations.
Titration Curves for Complex Acid/ Base Systems.
Applications of Neutralization Titrations.
Complexation Reactions and Titrations.
Agentometric titrations.
CHE21M2 Topics continued...
Electrochemical Methods of Analysis
•Introduction to Electrochemistry
•Applications of Standard Electrode Potentials
•Balancing redox equations.
•Redox titrations and applications of Redox titrations
•Iodimetry and iodometry
•Potentiometry
•Faraday’s laws of electrolysis
•Electrogravimetry and Coulometry
•Cyclic Voltammetry

Atomic Spectroscopy
•Atomic Emission Spectroscopy
•Atomic Absorption Spectroscopy
Statistics and Chemometrics for Analytical Chemists
Understanding ‘basic’ Chemometrics terminology
Precision versus Accuracy
Random errors versus Systematic errors
Quality planning
Quality assurance versus Quality control
Quality improvement
Quality management
Quality Control charts e.g., Shewhart charts, X-bar charts,
Range charts and S-charts (std devn charts).
Chemical standards and reference materials
Reference material and certified reference material
Q-test
Textbook: Statistics and Chemometrics for Analytical Chemistry, 4th edn by Miller & Miller
Test 2 will be written on Monday 29 October 2018.
Time: 8-10 am or 3-5 pm
Venue: First year Chemistry lab
 Some more important definitions in Statistics
Mean, x-bar: is ∑x divided by n, where n is number of data.
Mode is the score that occurs with the highest frequency. If
no value occurs more than once, then there is no mode.
When there is a tie between two values for the greatest
count, the data is said to be bimodal.
Median occupies the middle position after all the values
have been arranged in an ascending or descending order.
Sample Population

Symbols usually use lowercase Symbols usually use Greek letters

italic letters or capitals

x-bar for sample mean μ for population mean

s for sample standard deviation σ for population standard deviation

n for sample size (a lot smaller) N for population size (much bigger)
 Summary on measures of central tendency
Type of average Advantages Disadvantages

Very large or very small numbers can distort

Mean All the data is used to find the answer the answer. Hence NOT good for use with
distributions that have a few extreme scores.

1. Takes a long time to calculate median for a

very large set of data.
Unaffacted by very big and very small 2. Median does not take into account the precise
values. This means that the median is value of each observation and hence does
Median
NOT distorted by outliers or skewed data. NOT use all information available in the data.
3. Unlike mean, the median is not amenable
to further mathematical calculation and hence
is not used in many statistical tests.

1. There may be more than one mode.

2. There may be no mode at all if none of the
data is the same.
3. It may not accurately represent the data.

The mode is NOT used in statistical analysis

Mode The mode can be calculated easily.
as it is not algebraically defined and the
fluctuation in the frequency of observation is
more when the sample size is small.
Clearly, the mode is NOT a reliable measure
of central tendency.
 Choosing the most appropriate measure...
The mean is generally considered to be the best measure of
central tendency and hence it’s the most frequently used one.
However, be on the look-out as there are some situations
where the other measures of central tendency are preferred.

The median is preferred to mean when:

a) There are few extreme scores in the distribution.

b) Some scores have undetermined values.
c) There is an open ended distribution.
d) Data is measured in an ordinal scale.

Mode is the preferred measure when data is measured in a

nominal scale. Geometric mean is the preferred measure of
central tendency when data is measured in a logarithmic scale.
Quality – the degree to which a set of inherent characteristics
(i.e., of an intrinsic entity) fulfils given requirements.

Accuracy is the closeness of agreement between a

measured measurement and a true or accepted value of the
quantity being measured.

Precision is a measure of how well a result can be

determined. It is the degree of consistency and agreement
among independent measurements of the same quantity.

Repeatability: can the person producing the measurement

repeat in the future what he/she did in the past?

Reproducibility: can a second person reproduce the

measurement made by the first person?
Differences between accuracy & precision
Accuracy describes how closely the measurement from your
system matches the actual or true measurement of the thing
being measured. It is the difference between the observed
average of measurements and the true average.
Accuracy can be thought of as the “trustworthiness” of a
measurement system.

Precision describes how well a measurement system will

return the same measure; that is its repeatability.
It is important to be both accurate and precise if you are to get
useable information from your measurement system.
But the repeatability has two components - that of the
measurement system itself and that of the operator(s).
Differences resulting from different operators using the same
measurement device - this is called reproducibility.
 Accuracy and precision
Accuracy is the degree of conformity of a measured or
calculated quantity to its actual (or true) value.

Precision is the degree to which further measurements or

calculations show the same or similar results.

Thus, the precision of an experiment/object/value is a

measure of the reliability of the experiment, or how reproducible
the experiment is. The accuracy of an experiment/object/value
is a measure of how closely the experimental results agree with
a true or accepted value.
In summary,
Accuracy - The degree of closeness to accepted or true value.
Measurements - single
Precision – The degree to which an instrument or process will
repeat the same value. Multiple measurements are needed.
 Pictorial illustration of accuracy and precision...

A B

C D

B has very precise results but the mean is NOT accurate. C has
an accurate mean but the data points are imprecise. D is ideal.
Random Errors Systematic Errors

Random
Random errors Errors
in experimental measurements Systematic Errors
Systematic errors in experimental observations
are caused by unknown and unpredictable usually come from the measuring instruments.
Random errors in experimental measurements Systematic errors in experimental observations
changes inare
thecaused
experiment.
by unknown These changes
and unpredictable They
usuallymay
comeoccur because:
from the measuring instruments.
may occur in the measuring
changes instruments
in the experiment. or in
These changes there
They may is something wrong with the instrument or
occur because:
may occurconditions.
the environmental in the measuring instruments or in there
its is something
data handlingwrong with the
system, orinstrument or
the environmental conditions. its data handling
because system, or is wrongly used by the
the instrument
because the instrument is wrongly used by the
experimenter.
experimenter.
Random errors usually have a Gaussian
Random errors usually have a Gaussian
normal distribution
normal distribution

Examples ofExamples
causesofof random
causes errors
of random are:
errors are: Two types
Two types of systematic
of systematic error
error can can
occur withoccur with
instruments having
instruments a linear
having response:
a linear response:

electronic noise in the circuit of an electrical Offset or zero setting error - the instrument
electronic noise in the circuit of an electrical Offset or zero setting error - the instrument
instrument does not read zero when the measurant is zero.
instrument irregular changes in the heat loss rate from a does not read zero when the measurant is zero.
Multiplier or scale factor error in which the
irregular changes in thedue
solar collector heat loss rate
to changes from
in the wind.a Multiplier or scale factor
instrument consistently error in
reads changes in which
the the
solar collector due to changes in the wind. measurant ≥ than
instrument the actual changes.
consistently reads changes in the
measurant ≥ than the actual changes.
Precision is limited by random errors. The accuracy of measurements is usually
Random errors are usually determined by reduced by systematic errors.
Precision is limited by random errors. The accuracy of measurements is usually
repeating the measurements. Systematic errors are difficult to detect even for
Random errors are usually determined by reduced by systematic errors.
experienced research workers.
repeating the measurements. Systematic errors are difficult to detect even for
experienced research workers.
Random and systematic errors in routine analyses
In everyday analyses, one has to look-out for random and
systematic errors. For results to be accurate and precise,
random and systematic errors have to be kept at a minimum.

No stress … I deleted some ‘stuff’ here!

Repeatability and Reproducibility

Precision is estimated by making repeat measurements

on a sample under specified conditions. Repeatability
and reproducibility are different measurement conditions
which will give rise to different estimates of precision.

Repeatability conditions are when replicate

measurements are made in one laboratory, by a single
analyst, using the same equipment over a short time
period.

A common definition of reproducibility conditions is

when the replicate measurements are made by different
analysts, working in different laboratories, using different
equipment over an extended time period.
 Differences between repeatability and reproducibility...
Repeatability of measurements refers to the variation in
repeat measurements made on the same subject under
identical conditions. This means that measurements are
made by the same instrument or method, the same
observer (or rater) if human input is required, and that
the measurements are made over a short period of time,
over which the underlying value can be considered to be
constant.

Reproducibility refers to the variation in measurements

made on a subject under changing conditions. The
changing conditions may be due to different measurement
methods or instruments being used, measurements being
made by different observers or raters, or measurements
being made over a period of time, within which the ‘error-free’
level of the variable could undergo non-negligible
change.
Repeatability and Reproducibility
There is a subtle difference between "repeatability" and
"reproducibility"

(a) Repeatability includes neither drift errors (since consecutive

measurements over a period of time are too short for drift to be
a factor) nor hysteresis,

(b) Reproducibility includes drift (repeated measurements over

any length of time), hysteresis, and repeatability. Note that
reproducibility includes repeatability.

Know how to express this difference in your own words.

𝐬𝐭𝐝 𝐝𝐞𝐯𝐧
𝐂𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭 𝐨𝐟 𝐕𝐚𝐫𝐢𝐚𝐭𝐢𝐨𝐧 𝐂𝐕 = • 𝟏𝟎𝟎%
𝐱𝐛𝐚𝐫
Random errors – these cause replicate results to differ from
one another, so that the individual results fall on both sides of
the mean value. Random errors affect the precision or
reproducibility of an experiment. Random errors are statistical
fluctuations (in either direction) in the measured data due to the
precision limitations of the measurement device. Random
errors usually result from the experimenter's inability to take the
same measurement in exactly the same way to get exact the
same number. Systematic errors, by contrast, are
reproducible inaccuracies that are consistently in the same
direction. Systematic errors are often due to a problem which
persists throughout the entire experiment.
Note that systematic and random errors refer to problems
associated with making measurements. Mistakes made in the
calculations or in reading the instrument are not considered in
error analysis. It is assumed that the experimenters are
careful and competent!
How to minimize random errors
Take more data. Random errors can be evaluated through statistical
analysis and can be reduced by averaging over a large number of
observations.
Errors that can be reliably estimated by repeating measurements are called
random.
How to minimize systematic errors
Systematic errors are difficult to detect and cannot be analyzed statistically,
because all of the data is off in the same direction (either to high or too low).
Spotting and correcting for systematic error takes a lot of care.
Systematic errors are errors associated with a flaw in the equipment or in
the design of the experiment. Systematic errors cannot be estimated by
repeating the experiment with the same equipment. Consider again the
example of measuring an oscillation period with a stopwatch. Suppose that
the stopwatch is running slow. This will lead to underestimation of all our
time results. Systematic errors, unlike random errors, shift the results always
in one direction.
Systematic errors are much harder to estimate than random errors. After all,
how could we have known beforehand that our stopwatch was unreliable?
Quality and Quality Management

Quality planning – the part of quality management focused

on setting quality objectives and specifying necessary
operational processes and related resources for fulfilling the
quality objectives.
Quality assurance – the part of quality management focused
on providing confidence that quality requirements will be
fulfilled.
Quality control – the part of quality management focused on
fulfilling quality requirements.
Quality improvement – the part of quality management
focused on increasing the ability to fulfil the quality
requirements.
Quality management – coordinated activities to direct and
control an organization with regard to quality.
Differences between Quality Assurance and
Quality Control
Quality Assurance (QA) refers to the process used to create the
deliverables, and can be performed by a manager, client, or even a third-
party reviewer. Examples of quality assurance include process checklists,
project audits and methodology and standards development.
Quality Control (QC) refers to quality related activities associated with the
creation of project deliverables. Quality control is used to verify that
deliverables are of acceptable quality and that they are complete and
correct. Examples of quality control activities include inspection, deliverable
peer reviews and the testing process.

In other words,
Quality control is about adherence to requirements. Quality assurance is
generic and does not concern the specific requirements of the product
being developed.
Quality assurance activities are determined before production work begins
and these activities are performed while the product is being developed. In
contrast, Quality control activities are performed after the product is
developed.
Quality Assurance Quality Control

What: Prevention of quality problems through
planned and systematic activities including
documentation.
How: Establish a good quality management
system and the assessment of its adequacy
and conformance audit of the operation
system and the review of the system itself.
What: The activities or techniques used to
achieve and maintain the product quality,
process and service.
How: Finding and eliminating causes of quality
problems through tools and equipment so
that customer’s requirements are continually
met.

Quality Assurance is a complete system to
assure the quality of products or services. It is
not only a process, but a complete system
including also control. It is a way of
management.
Quality Control just measures and determines
the quality level of products or services. It is a
process itself.

Quality Assurance Quality Control

Process Product
Pro-active Reactive
Staff Function Line Function
Prevent the defects Find the defects
Quality Audit Walk through
Defining Process Testing
Selection of tools Inspection
Trainings Checkpoint Review
We provide more definitions of QA and QC because people
have different preferences. These definitions are ALL correct
because they come from qualitygurus.com so 1 is good enough.
QualityGurus.com gives many QA and QC definitions

Quality Assurance Quality Control

ISO 9000 Definitions

A part of quality management focused A part of quality management focused
on providing confidence that quality on fulfilling quality requirements.
requirements will be fulfilled.
Other definitions ...
QA is fundamentally focused on QC on the other hand is the physical
planning and documenting those verification that the product conforms
processes to assure quality including to these planned arrangements by
things such as quality plans, inspection, measurement etc
inspection and test plans.

QA is a system for evaluating QC is the process involved within the

performance, service, of the quality of
a product against a system, standard or
specified requirement for customers.
system to ensure job management,
competence and performance during
the manufacturing of the product or
service to ensure it meets the quality
plan as designed.
 Statistical Process Control
Control charts are one of the most commonly used methods of
Statistical Process Control (SPC), which monitors the
stability of a process. The main features of a control chart
include the data points, a centreline (mean value), and upper
and lower limits (bounds to indicate where a process output is
considered "out of control"). Control charts visually display the
fluctuations of a particular process variable, such as
temperature, in a way that lets the quality control chemist or
engineer easily determine whether these variations fall within
the specified process limits.
Because of time constraints, we will consider only one control
chart:
•Shewhart charts...named after Walter Shewhart who
developed them in 1924.
Remind me to highlight the Shewhart charts after the Test.
For Test 2 please ignore Shewhart charts!
 Major functions of a control chart
The main purpose of using a control chart is to monitor, control,
and improve process performance over time by studying
variation and its source.

There are several functions of a control chart:

1. It centres attention on detecting and monitoring process

variation over time.
2. It provides a tool for ongoing control of a process.
3. It differentiates special from common causes of variation in
order to be a guide for local or management action.
4. It helps improve a process to perform consistently and
predictably to achieve higher quality, lower cost, and higher
effective capacity.
5. A control chart serves as a common & effective language for
discussing process performance.
Key steps in plotting Quality Control charts

Some of the quality control charts require you calculate the

following:

•mean
•standard deviation (sample or population ... you decide!)
•position of warning limits (WLs)
•position of action limits (ALs)

𝟐 𝐬𝐭𝐚𝐧𝐝𝐚𝐫𝐝 𝐝𝐞𝐯𝐢𝐚𝐭𝐢𝐨𝐧
𝐖𝐚𝐫𝐧𝐢𝐧𝐠 𝐥𝐢𝐧𝐞𝐬 𝐚𝐫𝐞 𝐚𝐭: 𝐦𝐞𝐚𝐧 ±
𝐧

𝟑 𝐬𝐭𝐚𝐧𝐝𝐚𝐫𝐝 𝐝𝐞𝐯𝐢𝐚𝐭𝐢𝐨𝐧
𝐀𝐜𝐭𝐢𝐨𝐧 𝐥𝐢𝐧𝐞𝐬 𝐚𝐫𝐞 𝐚𝐭: 𝐦𝐞𝐚𝐧 ±
𝐧

n is the number of replicates

 Sample standard deviation versus
Population standard deviation
Sample standard deviation

The standard deviation of a sample is given a symbol s and is calculated using the following
equation:

x − mean 2
s=
n−1

Where x represents each value in the sample, x-bar is the mean value of the sample, ∑ is
the summation (or total), and n-1 is the number of values in the sample minus 1.

Population standard deviation

The standard deviation of an entire population is known as σ (sigma) and is calculated using
the following equation:

x− μ 2
σ=
N

Where x represents each value in the population, μ is the mean value of the population, ∑ is
the summation (or total), and N is the number of values in the population.
 Problem on a Shewhart chart Number of
Sample
defectives
A high-level computer technology has
developed bit-sized microprocessors for use in 1 5
2 6
operating industrial ‘robots’. To monitor the 3 4
fraction of defective microprocessors produced 4 7
5 1
by a manufacturing process, 50 6 3
microprocessors are sampled each hour. The 7 6
results for 20 hours of sampling are provided in 8 5
9 4
the Table on the right. In this problem, the 10 5
number of replicates is three. 11 8
12 3
13 2
(a) Show clear calculations of warning and 14 1
action lines. 15 0
16 1
(b) Plot the Shewhart chart for these results. 17 1
(c) Make concise comments on the Shewhart 18 2
chart you have just plotted. 19 3
20 3
Does the control chart indicate any out-of-control
signals?
Use these general guide-lines with care. Furthermore, these
guide-lines apply more to Shewhart charts than to other
charts.

A control chart indicates the presence of a problem in a

system when:

1. One or more points are on or outside the action limits.

2. Three successive points are outside warning limits but
inside action limits.
3. Two successive points are outside warning limits but
inside action limits on the same side of the mean.
4. Seven successive points are on one side of the mean.
5. Seven successive points are either increasing or
decreasing.
 Chemical Standards and Reference Materials
A reference material (RM) is a material or substance, one or
more properties of which are sufficiently well established to be
used for the calibration of a method, or for assigning values to
materials.

A certified reference material (CRM) is a reference material,

one or more of whose property values are certified by a
technically valid procedure, accompanied by or traceable to a
certificate or other documentation which is issued by a
certifying body.
Chemical standards are simply chemicals (usually single
chemicals) for which the purity is well characterized. Chemical
standards may be used for external calibration (where they are
measured in isolation from samples) or internal calibration (the
standard is added to the sample and the standard + sample
measured as a single ‘enriched’ sample).
 Chemical Standards and Reference Materials

Certified reference materials have five main uses:

1. Calibration and verification of measurement processes

under routine conditions.

2. Internal quality control and quality assurance schemes.

3. Verification of the correct application of standardised

methods.

4. Development and validation of new methods of

measurement.

5. Calibration of other materials.

 Q-test for outliers
We did many examples in class, but briefly here are the steps
to follow:
Step 1: Arrange the numbers in order of increasing magnitude.
Your suspect of outliers is on the boundaries, so apply the Q
test there.
Step 2: Calculate the range. Range = max – min. On the basis
of your suspect, calculate the gap.
Gap = Modulus of (suspect – its nearest neighbour)
Step 3: Determine Qcal
Qcal = gap/range
Step 4: Taking the number of observations (n) into account,
compare Qcal and Qtab at the specified confidence level.
Step 5: If Qcal > Qtab suspect is an outlier therefore reject it
otherwise retain it. Qtab is the (critical) value of Q tabulated in
the Statistical tables considering n and the specified confidence
level.
 Second year Electrochemistry topics

Electrochemical Methods of Analysis

Introduction to Electrochemistry.
Applications of Standard Electrode Potentials.
Ecell = Ecathode - Eanode
From thermodynamics, ΔG = - RTlnK and ΔG = - nFEcell
The Nernst equation
Balancing redox equations in acidic, alkaline and unspecified
conditions.
Redox Titrations
Make sure you know how to do the necessary calculations in
redox titrations, including the plotting of the graph.
Applications of Redox Titrations.

Potentiometry and Electrogravimetry

 Balancing Redox Equations

Be on the look-out for balancing redox equations in basic

medium ... usually the basic medium is fairly challenging and
many students forget the neutralization step right at the end.

A problem on balancing redox equations

Complete and balance the following equations in the specified

medium:
-
(a) Mn2+(aq) + NaBiO3(s) → Bi3+(aq) + MnO4 (aq) [acidic solution]

(b) NO2-(aq) + Aℓ(s) → NH3(aq) + Aℓ(OH)4- (aq) [basic solution]

[10 marks + 10 marks]
Make sure the examiner will follow your logical steps.
 Redox Titrations...the basics

Be on the look-out for redox titrations.

A problem on the application of redox titrations

The lead in a 0.2000-g sample is precipitated as PbCrO4. The

precipitate is filtered, washed, and dissolved in acid, giving a
solution containing dichromate ions and lead ions. The
dichromate requires 15.50 ml of 0.100 M ferrous sulphate for
titration.

(a) Construct a balanced equation for the dichromate-Fe2+

reaction.

(b) Use your equation in (a) to calculate (correct to 1 decimal

place) the percentage of lead in the sample. Mr (Pb) = 207.2
 Redox Titrations

Questions on plotting graphs in redox titrations

Calculate the potentials after the addition of 10.00, 25.00,

49.00, 49.90, 50.00, 50.10, 51.00 and 60.00 mℓ of the reagent.
Where necessary, assume that [H]+ = 1.00 M throughout.

Cr3+ + e- ⇌ Cr2+ Eo = -0.408 V

Fe(CN)63- + e- ⇌ Fe(CN)64- Eo = +0.360 V

(a) 50.00 mℓ of 0.1000 M Fe(CN)63- with 0.1000 M Cr2+

(b) 50.00 mℓ of 0.0500 M U4+ with 0.0200 M MnO4-.

UO22+ + 4H+ + 2e- ⇌ U4+ +2H2O Eo = +0.334 V

MnO4- + 8H+ + 5e- ⇌ Mn2+ +4H2O Eo = +1.51 V
Major steps in the memo ... Plotting of Redox Titrations
There are three important regions in a redox titration:
before equivalence point
at equivalence point and
after equivalence (i.e., post-equivalence)

The couples to be considered in each region changes.

Before equivalence, you consider the couple in the conical

flask.
At equivalence you consider both couples ... the number of
electrons in each couple is very important.
After equivalence, you consider the couple from the burette,
i.e., the titrant.
For your tests and exams please study Chapters 19&20 in
Fundamentals of Analytical Chemistry 8th edn, Skoog et al.,
(2004).
 Equivalence points in Redox Titrations

Calculating Eeqv in tricky redox titrations

Calculate the equivalence potential in the following redox

reaction. Where necessary, assume that [H]+ = 1.00
throughout.

20.00 mℓ of 0.0500 M U4+ with 0.0200 M MnO4-.

UO22+ + 4H+ + 2e- ⇌ U4+ +2H2O Eo = +0.334 V

MnO4- + 8H+ + 5e- ⇌ Mn2+ +4H2O Eo = +1.51 V

Show all the steps in this calculation.

Your final answer is:

Plotting a more challenging graph in Redox Titrations

The number of electrons in the two couples is different!

Calculate the potentials after the addition of 5.00, 15.00, 24.50,

24.90, 25.00, 25.10, 25.50 and 30.00 mℓ of the reagent. Where
necessary, assume that [H]+ = 1.00 throughout.

V3+ + e- ⇌ V2+ Eo = -0.255 V

Sn4+ + 2e- ⇌ Sn2+ Eo = +0.154 V

(a) 25.00 mℓ of 0.2000 M V3+ with 0.1000 M Sn2+

(b) 25.00 mℓ of 0.0500 M Fe2+ with 0.0100 M MnO4-.

Fe3+ + e- ⇌ Fe2+ Eo = +0.771 V

MnO4- + 8H+ + 5e- ⇌ Mn2+ +4H2O Eo = +1.51 V
Redox processes involving iodine ... Iodometric titrations

There is an important distinction we need to make concerning

iodimetry and iodometry.
Iodimetry (direct iodometric titration method) – refers to
titrations with a standard solution of iodine.
Iodometry (indirect iodometric titration method) – deals with
the titration of iodine liberated in chemical reactions.
In most iodometric titrations, the tri-iodide ion is formed when
an excess of iodide ion is present:

I2 (aq) + I- ⇌ I3-

Strictly speaking, all equations involving reactions of iodine

should be written with the tri-iodide ion (I3-) rather than with
molecular iodine (I2). However, chemists use molecular iodine
for the sake of simplicity.
Problem on Iodometric titrations ... catch the idea!
A 30.00-L air sample was passed through an absorption tower
containing a solution of Cd2+ where H2S was retained as CdS.
The mixture was acidified and treated with 10.00 ml of 0.01070
M I2. After the reaction: S2- + I2 → S(s) + 2I-
was complete, the excess iodine was titrated with 12.85 ml of
0.01344 M thiosulphate (S2O32-). Calculate (correct to 3 sig figs)
the concentration of H2S in ppm (mg per kg of sample). You
may want to use 1.20 g/L for the density of the gas stream. [20
marks]

Please note that ppm = μg/g = mg/kg = mg/L so when you use
ppm be clear on your units, that is, are you saying mg/kg or
mg/L?
Key steps in the memo ... Iodometric titrations

We will do this one together in class after Test 2!

Please remind me during the revision.

Electrogravimetry and Coulometry
Faraday’s laws of electrolysis
Michael Faraday did a lot of research on electrolysis and he
came to the conclusion that during electrolysis, the quantities of
substances liberated at electrodes depended upon the
following three factors:
1. The quantity of electricity passed
2. The duration (time) of passing the current at a uniform rate
3. Charge on the ions being liberated.
First law: The mass of an element liberated on an electrode
during electrolysis is directly proportional to the quantity of
electricity (Q) which passes through a solution of an electrolyte.
Q = It [One Faraday = 96 485 Coulombs per mole of electrons]
Second law states that when the same quantity of electricity is
passed through several electrolytes, the mass of the
substances deposited are proportional to their respective
chemical equivalent or equivalent weight.
Faraday’s laws of electrolysis ... continued
Chemical equivalent = atomic mass of element/element valency

Problem of Faraday’s laws of electrolysis

(a) A Cr3+(aq) solution is electrolyzed, using a current of 7.60 A.

Calculate the mass of Cr(s) that is plated out after 2 days.

(b) What amperage is required to plate out 0.250 moles of Cr from a

Cr3+ solution in a period of 8.00 hours?
Coulometry

Coulometry and Electrogravimetry are closely related methods

in which electrolysis is done for a sufficiently long time to
ensure complete oxidation or reduction of an analyte to a
product of known composition.

In coulometric techniques, the amount of analyte is determined

by measuring the quantity of electrical charge needed to
completely convert the analyte to a product.

Calculations in coulometry-based questions involve the use of

moles relations, stoichiometry and Faraday’s laws of
electrolysis especially, Q = It
From coulombs go to Faradays and relate the Faradays to the
stiochiometry of the balanced equation. Refer to the question
in the next slide.
Coulometry-based question ...

The nitrobenzene in 194 mg of an organic mixture was

reduced to phenylhydroxylamine at a constant potential of -0.96
V (vs. SCE) applied to a mercury cathode:

C6H5NO2 + 4H+ + 4e- → C6H5NHOH + H2O

The sample was dissolved in 100.0 ml of methanol; after

electrolysis for 30 minutes the reaction was judge complete. An
electronic coulometer in series with the cell indicated that the
reduction required 31.23 Coulombs.

Calculate (correct to 3 sig figs) the percentage of C6H5NO2 in

the sample.