Lab Manual

Schooll of Enggineeringg & Phyysical Sciences
S s
Chemiccal Engiineeringg
Chhemicaal Enggineeering Labor

L ratoryy Man
nual
Y 1
Year
Acaddemicc Yeaar 20112/13
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Contents
Introduction 4
Aims of the Laboratory Sessions 5
Attendance 5
Lab Organization 5
Safety 6
Record of Experimental Work: Lab Notebook 7
Assessment 8
Report Submission 8
Late Penalties 9
Plagiarism 9
Marks 10
Feedback 10
Experimental Rota 11
Handling Numerical Data 12
Consideration of Accuracy and Errors 14
Standard deviation 16
Log-Log and Log-Linear Graph Plotting 18
Logarithmic Scales 18
Determining the equation of a line 19
Determining the gradient of a log-log graph 20
Experiment 1. Gases: Determination of the Molar Mass of a Gas 22
Experiment 2. Solutions: Determination of the Molar Mass of a Solute from
Freezing Point Depression Measurements 25
Experiment 3. Thermochemistry: Thermochemistry and Hess’s Law 29
Experiment 4. Chemical Kinetics: The Iodine Clock 32
Experiment 5. Equilibrium Constant: Determination of an Equilibrium
Constant 36
Experiment 6. Acids and Bases: Determination of Concentration using
Titration 41
Experiment 7. Spectroscopic Analysis of a Heavy Metal Contaminant: Cobalt
in Water 44
Experiment 8. Effect of Pressure on Boiling Point/Boiling Point Elevation by
Dissolved Salts 48
Experiment 9. Verification of Boyle’s Law and the determination of the molar
volume of air at S.T.P. 51
Experiment 10. Flash Point using the Pensky-Martens Apparatus 53
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Experiment 11. Determination of the Thermal Properties of Water 57

Experiment 12. Specific Volume/Density Changes of Water as a Function of
Temperature 60
Appendix I. Layout of Laboratory Reports 62
Appendix II. Location of Experiments 64
Appendix III. More Information on Significant Figures, Accuracy and Errors 65
Significant Figures 65
Scientific Notation 65
Significant Figures in Calculations 65
Rounding 66
Estimating Combined Errors 67
Appendix IV. Calibration of a PH meter 72
Appendix V. Indicator Colours 73
Appendix VI. Shimadzu UV mini-1240 Spectrophotometer 74
Appendix VII. Unicam Heλios Spectrophotometer 75
Appendix VIII. Density Bottle Principles 77

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INTRODUCTION
This laboratory course will introduce you to basic practical physical chemistry and chemical
engineering. You will gain essential experience in making careful experimental measurements and
in critically analysing the data obtained. The experiments relate to topics in physical chemistry and
chemical engineering, but, in some cases, the relevant lectures follow the practical work. To allow
for this, each experiment contains a description of the related principles as well as the experimental
procedure. In this manual you will find instructions for each of the experiments.
We want you to enjoy your time in the lab. One of the best ways to ensure this is to prepare properly
for each experiment by reading the lab manual before you enter the lab. This will help you to
organize your time as effectively as possible.
THE ONE, SINGLE THING THAT WILL IMPROVE YOUR LAB EXPERIENCE IS TO
READ THE LAB MANUAL BEFORE STARTING THE EXPERIMENT
This is what you should do:

Before the lab session, find out which experiment you have been assigned (this can be found on
Vision) and read through the instructions in the lab manual. At this stage you should also refer to
any book references that have been provided for the experiment. This will ensure that you are more
familiar with both the method and the theory of the experiment before starting the practical session.
During the lab session, neatly record all results and/or observations in your laboratory notebook.
After the lab session, write-up the experiment in the manner indicated in this manual and complete
any questions or exercises which follow.
However, we do not expect you to understand all of the chemistry by yourself. To help you, a team
of postgraduate demonstrators will be on hand throughout the term. A demonstrator will be assigned
to you and you should approach him/her in the first instance with any questions you may have. In
addition, a member of academic staff will always be in the lab as well as a member of the technical
staff and you should also feel free to approach these people at any time if you have any questions.
DEMONSTRATORS AND MEMBERS OF STAFF ARE HERE TO HELP YOU.

IF IN DOUBT, ASK!
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Aims of the Laboratory Sessions
¾ To train you in key practical skills, including data analysis
¾ To train you in (a) laboratory note taking and (b) report production
¾ To reinforce the chemistry and chemical engineering that you encounter in first year lectures.
¾ To encourage you to develop organisational and time management skills – in particular how to
meet deadlines for reports etc.
¾ To encourage you to think about experimental data and results, and their significance/relevance.
Attendance
You must attend all laboratory classes and attendance will be monitored. An attendance list will be
available for the first and last fifteen minutes of the laboratory session and must be signed upon
entering and prior to leaving the laboratory. If you are late, consult the member of staff on duty.
Absence from a practical session is excused only with good cause. As with any absence, medical
certificates must be presented to your year Director of Studies immediately on your return to the
University. In addition, you must inform the member of staff in charge of the laboratory that you
have done so at the first available laboratory session.
Lab Organization
The lab sessions will run on Thursdays from 2.15 to 5.15 pm in Weeks 9, 10 and 11 of semester 1
and weeks 1 to 3 of semester 2. In these weeks, working in groups, you should complete six
experiments at a rate of one experiment per week. The order in which you will do these experiments
is shown in the rota provided on page 11 of this manual. The practical work associated with each
experiment must be completed during the 3 hour session. If you finish your experiment within the
time period allocated do not proceed to the next experiment, but make sure you have made a note of
all the information you need to write your report.
All glassware and equipment needed for experiments in WP 2.25 is to be found

either on the designated bench or in the appropriate locker (see Appendix II).
When you have completed the experimental work, please wash all glassware,
place it in the tray provided and return it to the experiment lockers. For
experiments in JN G46, clean all the equipment and return it to the bench.
LEAVE THE LABORATORY IN THE CONDITION YOU FOUND IT.
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Safety
1. You will have been issued with a copy of the School Taught Course Safety Handbook at the
start of the year, and an electronic version is also available on Vision. Please read and
understand the safety procedures. You will be asked to sign an acceptance form stating that
you have read the booklet, are aware of procedures and will comply with them. This must be
done before the first laboratory session!
2. You are required to wear laboratory coats and safety glasses while in the laboratories, and
where necessary gloves. These can be provided at the start of each laboratory, if you don’t
have personal ones, and should be returned at the end of each laboratory period.
3. For safety reasons, laboratory work may only be carried out during the specified periods,
unless prior permission has been given by the laboratory supervisor and/or experiment
supervisor. Similarly we do not want to see piles of bags and coats, etc in the lab areas.
Come prepared to do the experiment with writing implements, lab book, text books, etc.
Bags, etc. can be placed in a locker. If you don’t have one, then you can obtain one through
the Nasmyth Stores, if any are available.
4. By law, ALL activities in the workplace must be assessed for any potential risks. Therefore
all experiments will have fixed on them (or nearby) a form noting potential risks relating to
that experiment. READ!! before operating equipment. If you have any queries, ask the
supervisor.
5. As a part of the risk assessment mentioned in item 4 above there are regulations involving
the Control of Substances Hazardous to Health (COSHH). Any substance designated VERY
TOXIC, TOXIC, CORROSIVE, HARMFUL, IRRITANT, and to this we will add
FLAMMABLE, must have a written risk assessment and, where necessary, an approved
"scheme of work" compiled for its use. You must, where necessary, familiarise yourself with
this "scheme of work" and follow it.
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6. In addition to item 4 above, ALL chemicals used have Material Safety Data Sheets available.
Read these sheets BEFORE using ANY chemicals, paying particular attention to safe
handling and emergency procedures.
(Note: This is a procedure you should be adopting as a general

rule in your career, whenever and wherever you are
working with any form of chemical.)
7. Make sure that you understand the operation of any piece of equipment before starting
experimental work.
8. Any defects in and / or breakage of equipment should be reported immediately to the

experiment supervisor.
9. Disposal of glass, chemicals and solvents:

• Glassware must be rinsed free of contaminating chemicals (with acetone for example) before
disposal.
• Any waste glass must be disposed of in the containers provided. Do not leave sharp edges
protruding from the containers.
• Solvents must be disposed of in the appropriate waste solvent container. Never put solvents
down the drain. Never put any chlorinated solvents in a non-chlorinated waste container.
• Non-reactive/non-hazardous solid materials must be disposed of as instructed.
• If in doubt – check with a demonstrator first.
• NEVER PUT ANY WASTE GLASS OR CHEMICALS IN THE WASTEPAPER BINS.
Record of Experimental Work: Lab Notebook
The essence of good experimental work in any discipline is careful observation and good note
taking. Initially, experimental observations and data can be recorded in a shorthand notebook.
NEVER use odd pieces of paper for this purpose. Make sure you record all the information
necessary to write-up, retrospectively, a full report on any experiment. If you are not certain
whether you will need a particular piece of information, make a note of it anyway; you don’t want
to find that a key fact is missing when you write up.
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Assessment
Practical work will be assessed throughout the course by inspection of your laboratory notebook
each week and by assessment of written reports. Since the laboratory mark total contributes the
majority of coursework marks for Process Industries A/B B47AA1/B2, it is vital that you write up
reports quickly and submit them on time.
Formal Reports. Formal reports are required for all experiments. These should be produced using a
word processor and printed on A4 size paper. Guidance on how to produce your formal report is
given in Appendix I.
Report Submission
Each formal report must have a signed copy of the supplied cover sheet (available on Vision), with
the experiment title and details of when the report was submitted. Reports should be submitted
before 2.15 p.m. on the Thursday after the week during which the experiment was performed.
Reports should be deposited in the submission box in the Nasmyth Crush Area. No extension will
be granted, except for certificated medical reasons. Reports will be collected from the box shortly
after the submission deadline. Any report submitted after the initial collection will be recorded as
late and suffer a late submission penalty.
Late Penalties:
If you are late a penalty will be applied unless you have a valid mitigating circumstance. IT related
problems such as lost computer files, or a broken computer, do not constitute a valid excuse; you
should get into the habit of making an independent backup of your work so that even if such events
do happen you can still deliver coursework on time. Keep an electronic copy of all coursework; it
will also be useful if paper copies are lost or damaged.
After five working days (normally a week) it will be at the discretion of the supervisor if the report
is accepted, otherwise you technically fail the course because all coursework must be submitted in
order to pass, irrespective of overall mark. It will then be classed as remedial work that goes towards
your resit requirements (for which you will have to pay the resit fee). However, if it is accepted, it
will only be classed as pass or fail, which in practice means that the maximum available mark will
be capped at 40% and the actual mark could be lower.
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Moral of the situation? DON’T BE LATE!!!
There will be no exceptions, other than in very extreme circumstances, but there will need to be
good evidence. If it was an emergency nobody is going to complain.
Plagiarism
Copying of experimental data, calculations or other material from your fellow students or any other
source is forbidden and is considered to be a serious offence. This includes copying of unattributed
material from internet sources. If any plagiarism is detected you will receive no marks for the
experiment, as will the person from whom the material was copied, and a formal disciplinary report
will be submitted to the Head of School.
Marks
Each report will be marked according to the marking criteria. A percentage score will be awarded
and equated to a grade in the range A-F, with A equating to excellent down to F which equates to
fail. Reports for which the author has clearly not made a satisfactory attempt to complete the
report will be returned unmarked. After assessment insert your report into the appropriate part of
the laboratory manual to provide a complete record of that particular experiment.
1. Report Layout – the requirements for Chemical Engineering laboratory reports are provided in
Appendix I.
2. General Presentation of Report - the report MUST be typed. Tidiness, legibility, spelling,
English, conciseness will also be considered.
3. Accuracy of account - for example: the inclusion of important experimental detail (e.g. the
molarity of chemical solutions used).
4. Accuracy of the experimental data.
5. Ability to convert experimental data to a more useful or standard form, e.g. conversion of
pressure units indicated on gauges to standard S.I. units.
6. Appreciation of significance of the results obtained - particularly in the discussion section of the
report. Comparison with theory, appreciation of errors.
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7. Ability to draw concise and valid conclusions based on reasoning in the Discussion Section.
8. Promptness in handing in reports. Late reports may not be marked, however any that are will get
a mark penalty
Feedback
Each marked report will be returned with a feedback on a pre-designed sheet. Use the feedback to
learn and improve your next report. Feedback from one report to the next will be analysed to see if
you are taking the advice.
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Experimental Rota
Semester 1 Semester 2
Group Week 9 Week 10 Week 11 Week 1 Week 2 Week 3
1 1 2 3 4 5 6
2 1 2 3 4 5 6
3 1 2 3 4 5 7
4 2 3 4 5 6 7
5 2 3 4 5 6 8
6 2 3 4 5 7 8
7 3 4 5 6 7 9
8 3 4 5 6 8 9
9 3 4 5 7 8 10
10 4 5 6 7 9 10
11 4 5 6 8 9 11
12 4 5 7 8 10 11
13 5 6 7 9 10 12
14 5 6 8 9 11 12
15 5 7 8 10 11 1
16 6 7 9 10 12 1
17 6 8 9 11 12 1
18 7 8 10 11 1 2
19 7 9 10 12 1 2
20 8 9 11 12 1 2
21 8 10 11 1 2 3
22 9 10 12 1 2 3
23 9 11 12 1 2 3
24 10 11 1 2 3 4
25 10 12 1 2 3 4
26 11 12 1 2 3 4
27 11 1 2 3 4 5
28 12 1 2 3 4 5
29 12 1 2 3 4 5
The table contains the experiment number. Experiments 1 to 7 are located in WP 2.25, while
experiments 8 to 12 are located in JN G46. Please make sure you know where you will be
working.
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Handling Numerical Data
Experiments in physical chemistry involve acquiring data, followed by data manipulation and
analysis. The brief description given below should be read carefully and applied to your
experimental data.
Precision and accuracy
In any series of measurements, the measured qualities are obtained to a certain degree of precision.
Precision refers to the closeness of the set of values obtained from identical measurements of the
quantity. Accuracy refers to the closeness of a single measurement to its true value.
To illustrate the idea of precision, consider lengths obtained using a ruler graduated in millimetres.
One person measures an object to be 9.12 cm. Two others record the result as 9.11 and 9.13
respectively. Clearly there is some uncertainty about the last digit even if the average of the results,
9.12 cm, is quoted. In this example the last digit in the reported measurement is assumed to be
uncertain by ±1. This convention only gives an approximate indication of the precision but probably
underestimates the confidence range within which the true value lies. A statistical approach to the
determination of precision is given in the experiments on Gases and on Chemical equilibrium.
Significant figures
The phrase “number of significant figures” refers to the number of digits reported for the value of a
measured or calculated quantity, indicating the precision of the value. To count the number of
significant figures in a given quantity, observe the following rules.
1. All digits are significant except zeros at the beginning of the number and possibly terminal
zeros (one or more zeros at the end of a number). Thus, 9.12 cm, 0.912 cm and 0.00912 cm
all contain three significant figures.
2. Terminal zeros ending at the right of the decimal point are significant. Each of the following
has three significant figures: 9.00 cm, 9.10 cm, 90.0 cm.
3. Terminal zeros ending to the left of the decimal point may or may not be significant. When a
measurement is given as 900 cm, we do not know whether one, two or three significant
figures were intended unless it is explicitly stated. Any uncertainty can be removed by
expressing the measurement in scientific notation.
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Scientific notation
n
Scientific notation is the representation of a number in the form A x 10 , where A is a number with a
single non-zero digit to the left of the decimal point, and n is an integer, or whole number. In
scientific notation, the measurement 900 cm precise to two significant figures is written 9.0 x 102
cm. If precise to three significant figures, it is written 9.00 x 102 cm. Scientific notation is also
convenient for expressing very large or very small quantities. It is much easier (and it simplifies
calculations) to write the speed of light as 3.00 x 108 (rather than as 300,000,000) metres per second.
Significant figures in calculations
How do we report the significant figures in a calculation? Suppose we measure the solubility of a
substance; we find that 0.0634 g of the substance dissolves in 25.31 g of water. The amount
dissolving in 100.0 g is
(100.0 gwater)
(0.0634g)x
(25.31 gwater)
Doing the arithmetic on a pocket calculator, gives 0.2504938. But it would be incorrect to give this
number as the final answer, because it is much more precise than the other numbers in the
calculation.
In multiplication or division of measured quantities - give as many significant figures in the

answer as there are in the measurement with the least number of significant figures. In the above
calculation, 0.0634 g has the least number of significant figures (three), and so here the answer
should be reported to three significant figures, that is, 0.250 g.
In addition or subtraction of measured quantities - give the same number of decimal places in the
answer as there are in the measurement with the least number of decimal places. Consider
addition of 184.2 g and 2.324 g. 184.2 + 2.324 = 186.524. But because the quantity 184.2 g has
only one decimal place (while 2.324 g has three) the answer should be reported as 186.5 g.
Any number whose value is known exactly does not affect the number of significant figures in a
result. For example, there are 12 inches in 1 foot. The number 12 is known exactly, so (12
inches/foot) x (3.16 feet) = 37.9 inches. The number of significant figures is determined by 3.16, not
12.
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Rounding
Rounding is the procedure of dropping non-significant digits in a calculated result and adjusting the
last digit reported. The general procedure is as follows. Look at the leftmost digit to be dropped.
1. If this digit is greater than 5, or is 5 followed by non-zeros, add 1 to the last digit to be
retained and drop all digits farther to the right. Thus rounding 1.2151 to three significant
figures gives 1.22.
2. If this digit is less than 5, simply drop it and all digits farther to the right. Rounding 1.2143
to three significant figures gives 1.21.
3. If this digit is 5 or 5 followed by zeros, and if the last digit to be retained is even, just drop
the 5 and any zeros after it. If the last digit to be retained is odd, add 1 to it and drop the 5
and any zeros after it. For example, rounding 1.225, 1.22500 and 1.21500 to three significant
figures gives 1.22 in each case.
In a calculation of two or more steps, retain additional digits for intermediate answers so that small
"rounding" errors do not appear in the final result. If you use a calculator, simply enter numbers one
after the other, perform each arithmetic operation and round just the final answer.
Consideration of Accuracy and Errors
(More information on this topic is available in Appendix III.)
When making a scientific measurement it is always necessary to assess its accuracy. If this is not
done the result has very little meaning. It is therefore very important to be clear about how many
figures are significant in any quantity you measure or calculate and to make this clear in any reports
that you write.
In any series of measurements, the measured qualities are obtained to a certain degree of precision.
Precision refers to the closeness of the set of values obtained from identical measurements of
the quantity. Accuracy refers to the closeness of a single measurement to its true value.
Suppose in an experiment you wish to determine a pressure at 0°C in S.I. units to 4 significant
figures by measuring the height of a column of mercury. At some point in the calculation you will
require the density of mercury and it will obviously be necessary to know it to the required
accuracy. One might find a value of 13.6 g cm-3 quoted but this is not specific enough. It might
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mean that the result is accurate to 3 significant figures, or that this is an average value in which there
is a great deal of uncertainty in the final figure (e.g. (13.6 ± 0.3) g cm-3) or it might conceivably
mean that the density is 13.6 g cm-3 exactly, i.e. 13.6000 etc. It is much more useful to have the
result quoted with an estimate of the error. An accurate value of this quantity might be quoted as
(13.595 ± 0.001) g cm-3. The meaning of the result is now quite clear.
It is also necessary to know how a certain error in each of a number of measured quantities affects
the accuracy of another quantity derived from them. To continue with the same example, the
pressure is given by:
P = ρgh
Suppose measurements of ρ, g and h have given the following results:
ρ = (13.595 ± 0.001) g cm-3 = (1.3595 ± 0.001) 104 kg m-3
h = (0.1124 ± 0.0002) m
g = (9.811 ± 0.001) m s-2
Then
P = 14.9920 x 103 N m-2
and we wish to estimate the accuracy of P. One obvious way of doing this is to take the extreme
values of the quantities ρ, g and h and see what values of p result. If we take the maximum values
of ρ, g and h we get the largest possible result for p and conversely the minimum values give the
smallest P. A good deal of numerical work is saved, however, if the calculus is used:-
P = ρgh
dP = h g dρ + g ρ dh + h ρ dg
dP/P = dρ/ρ + dh/h + dg/g
= 0.0001/1.3595 + 0.0002/0.1124 + 0.001/9.811
= 0.00195
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∴ dP = 0.002 x 14.9920 x103 = 0.03 x 103
P = (14.99 ± 0.03) x 103 Nm-2
As a second example, consider the calculation of a density ρ, from the measurements of mass, M,
and volume, V.
ρ = M/V
Then,
dρ = dM/V – M dV/V
dρ/ρ = dM/M – dV/V
In using this formula we must remember the dM and dV are errors in independent quantities M and
V. They may then be opposite in sign. To estimate the largest possible error in ρ, therefore, we
must consider the situation when dM is +ve and dV is – ve. Hence in formulae such as the above
the signs are generally all taken as positive. Hence if,
V = (5.01 ± 0.04) cm3

and M = (0.245 ± 0.001) g
ρ = 4.8902 x 10-2 g cm-3
dρ/ρ = 0.001/0.245 – (-0.04)/5.01
dρ = 0.00059 = 0.059 x 10-2 g cm-3
ρ = (4.89 ± 0.06) x 10-2 g cm-3
Standard deviation
In the foregoing discussion we have used terms like accuracy, maximum error, probable error etc.
rather loosely. If a large number of measurements of some quantity have been made then precise
definitions of certain quantities measuring the error can be given in terms of the scatter of results.
For example, suppose a length is measured six times and is found to have values:- 2.0, 2.1, 2.1, 2.0,
2.0, 1.8cm.
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The average value,
(2.0 + 2.1 + 2.1 + 2.0 + 2.0 + 1.8)/6 = 2.0
We may now try to define the accuracy in terms of a mean error. If we simply take the mean
deviation
(0.0 + 0.1 + 0.1 + 0.0 + 0.0 – 0.2)/6 = 0
We get the answer zero from the definition of the average. In measuring an ‘average’ error it is
clearly wrong to have positive and negative errors cancelling out, since in that way we can get a
very large spread of results and still get zero for our error measurement! Hence the quantity usually
considered is proportional to the sum of the squares of the errors, which is always positive.
If we have l results for the measurement, l1, l2, ….ln and l is their mean then the quantity
n
( )
∑ l− l
2
σ= l
is a measure of the mean error. This quantity is known as the standard deviation. It can be shown
mathematically that if there is purely random distribution of errors then 50% of all results obtained
will be within the limits (l ± 0.675 α), 68.2% within (l ± α) and 95.4% within (l ± 2α The error
corresponding to the first of these ranges (± 2/3 α), is sometimes known as the probable error, since
the probabilities of a single result being within the range and outside it are equal.
If a large number of measurements (>10) are available then the standard deviation and probable
error should be calculated. For smaller numbers of results the statistical analysis has no precise
meaning and an ‘error’ can be estimated by inspection of the spread of results.
REFERENCE
J. Topping, ‘Errors of Observation and their Treatment’, (Institute of Physics Monographs for Students).
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LogLog and LogLinear Graph Plotting
Power functions of the form:

y = a.xb
plotted directly on to log-log graph paper give a straight line. Similarly when experimental
functions such as:
y = a.10bx or y = a.ebx
are plotted on log-linear graph paper, a straight line results.
Thus log-log and semi-log papers can be used for plotting straight lines of power and exponential
functions respectively without the need to calculate logarithms of the x and y values.
Logarithmic Scales
On log-log paper, both the abscissa and the ordinate have logarithmic scales. Linear distances are
therefore proportional to the logarithms of the graduated co-ordinate scales rather than the numbers
themselves. Semi-log paper has a logarithmic ordinate and a linear abscissa (which is always used
to represent the value of the exponent x).
Logarithmic axes are divided into one or more equally sized repetitions called CYCLES. Each
cycle represents an increase by a constant factor (usually 10) in the quantity represented. The cycles
are logarithmically subdivided into 10 major divisions that represent multiple increases of x 2 to x 9
in the quantity.
When using logarithmic paper, it is important to select paper that has the most appropriate number
of cycles on each axis of the graph that is to be plotted. For log-log graphs, the number of cycles (nx
and ny) is determined by rounding up to the nearest whole numbers, the results of the following
calculations:
ny = log(ymax/ymin) and nx = log(xmax/xmin)
where the subscripts ‘max’ and ‘min’ refer to the maximum and minimum values of the data set.
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Example 1
The number of cycles needed to plot a graph of the following data set is determined as follows:
x 1 2 5 10 20 50
y 0.50 1.41 5.59 15.81 44.72 176.8
ny = log(ymax/ymin) = log (176.8/0.5) = 2.548 = 3 cycles on ordinate

nx = log(xmax/xmin) = log(50/1) = 1.699 = 2 cycles on abscissa
The graph therefore should be plotted on ‘log 3 cycles x 2 cycles’ graph paper. When choosing
paper to use it is done by choosing “log y cycles x log x cycles”.
A similar procedure is followed for exponential plots on semi-log paper, but only ny needs to be
determined.
Determining the equation of a line
If a data set produces a straight line on a log-log or semi-log graph plot, the values of the equation
constants can be determined.
For the power functions where y = axb:
ln y = ln a + b ln x
and
b = ln y2 – ln y1/ln x2 – ln x1
Furthermore, when y = 1
ln a = -b ln x
Example 1a
The equation of the plotted line of the data set in example 1 is determined as follows:
ln y = ln a + b ln x
b = ln 176.8 – ln 0.50/ln 50 – ln 1 = 1.50
When y = 1; x = 1.6
ln a = -1.5 ln 1.6 = 0.705
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The equation of the line is therefore

ln y = 0.705 + 1.5 ln x
y = 0.5x 1.5
For exponential functions where y = aebx:
ln y = ln a + b.x
and
b = ln y2 – ln y1/x2 – x1
Furthermore, when y = 1
ln a = -b.x
Determining the gradient of a loglog graph
Direct measurement, using a ruler, of the length of x and y components of the gradient in cm (mm or
in) from the ruler. Do not use the scales on the paper.
The more mathematical way,
Gradient = log y2 – log y1/ log x2 – log x1
Remember, there is no intercept on a log-log axes graph, as such, as x or y never reach zero. 10n are
the units, so whatever you put as n, you will never get zero). Therefore drawing a line to the y-axis
to find an intercept when x = 0 is technically incorrect.
Therefore having found the ‘best fit’ line and the gradient of the line, take a point from the line and
put values into the equation to find the intercept value.
e.g. equation is y = axb
A log-log graph will give b from the gradient, then take a point on the line and you now know x, y
and b. ∴a = y/xb.
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A similar situation also occurs with log-linear graphs for equations of the form
y = a10bx or y = aebx
If you take logs
log y = log a + bx or ln y = ln a + bx
the linear axis is always used to represent the x values, therefore the gradient would be
log ymax – log ymin/xmax - xmin.
21
Experiment 1 Page 22
Experiment 1. Gases: Determination of the Molar Mass of a Gas
Aim
To determine the molar mass (M) of a gas by measuring the volume occupied by a known
amount of gas at a known temperature and pressure.
Introduction
The ideal gas equation is:
pV = nRT (1)
where p is pressure, V volume, T temperature and n the number of moles of gas. Since n = w/M,
where w = mass of gas and M is its molar mass, it follows that:
wRT
M = (2)
pV
Thus, the molar mass can be determined if the temperature, pressure and volume occupied by a
known mass of gas are measured.
In this experiment, you will inject a weighed amount of liquid into a gas syringe which is heated
by a steam jacket. The liquid vaporizes and you will record its pressure, volume, and temperature
and hence determine M using equation (2).
Safety and Hazard Assessment
1. The liquids employed may be flammable. No open flames are allowed during the
experiment.
2. Dispose of any excess liquid in the flammable liquid residue bottle provided in the fume
cupboard.
22
Equipment and Apparatus
1. The gas syringe apparatus including a 500 ml round bottom flask and isomantle will have
been set up for you, before the start of the experiment.
2. Additional equipment to be found in the appropriate locker: 2 cm3 hypodermic syringe

with needle, small cork, self-sealing cap.
Procedure
1. Check that the boiling flask is half-full of water; if not, replenish with hot tap water. Switch
on the heating mantle. (You start the experimental measurements when the water is at
boiling temperature).
2. Rinse the inside of the hypodermic syringe with your unknown liquid sample, then draw
into it ~ 2 cm3 of the sample. Note the number of your unknown!
3. Dry the hypodermic needle, seal the needle with a small rubber or cork bung and weigh the
syringe, its contents and the bung using a 4-figure balance.
4. Remove the red self-sealing cap from the nozzle of the large gas syringe and set its volume
to ~ 5 cm3 (of air).
5. Refit the cap over the nozzle of the syringe and allow the steam to pass through the jacket
surrounding the gas syringe until the temperature is constant (~100°C).
6. Record the temperature and the volume of the air in the gas syringe.
7. Remove the bung from the hypodermic syringe and insert its needle through the self-
sealing cap on the gas syringe, making sure the needle tip is beyond the narrow nozzle.
8. Slowly inject the liquid into the gas syringe. The liquid will vaporize, pushing the syringe
barrel downwards. Inject sufficient to give a final volume of ~ 80 cm3.
9. Withdraw the hypodermic syringe and reseal it with the bung. Immediately record the
volume of air plus vapour in the gas syringe. The difference between this volume and that
in step 6 is the volume occupied by the vapour.
10. Reweigh the hypodermic syringe to obtain the mass of liquid injected.
23
11. Remove the self-sealing cap and reset the gas syringe to ~ 5 cm3.
12. Carry out steps 5 to 10 five times, reweighing the hypodermic syringe after each injection.
13. To carry out the calculation you will need to know the atmospheric pressure. Your
demonstrator will provide a value in mm of mercury, that needs to be converted it to Pa. (1
atm = 760 mm mercury = 101,325 Pa.).
Results
For each injection, calculate the molar mass of the vapour using equation (2). In this, the pressure
must be in Pa, the volume in m3, and the temperature in K. The value of the gas constant R is
8.314 J mol-1 K-1 (or 8314 J kmol-1 K-1).
Calculate the average value of M from your measurements.
Determine the standard deviation (σ) οf your result using the method described in Appendix III.
Give the number of your sample and report its molar mass as the average value ± σ.
24
Experiment 2. Solutions: Determination of the Molar Mass of a Solute
from Freezing Point Depression Measurements
Aim
The aim of this experiment is to determine the molar mass of a solute by measuring the
depression of the freezing temperature of a solution of the solute.

Introduction
When a non-volatile solute is dissolved in a liquid the freezing point of the resulting solution is
less than that of the pure liquid. This depression of the freezing point is proportional to the solute
concentration expressed in terms of molality (m). This is defined as the number of moles of
solute dissolved in 1000g of solvent. Thus:
∆T f = K f m (1)
where ∆Tf represents the depression of the freezing point and Kf is the molal depression constant
whose value depends on the solvent, but not on the solute. Kf is expressed in units of K kg mol-1.
When w2 g of solute of molar mass M2 is dissolved in w1 g of solvent, the molality is given by:
1000 w2
m= mol kg-1 (2)
w1M 2
Combining equations (1) and (2) gives:
1000 w2 K f
M2 = g mol-1 (3)
w1∆T f
where, to obtain solute of molar mass M2 in g mol-1, it is necessary that the molal depression
constant be expressed in K kg mol-1.
In this experiment, you will first determine the freezing temperature of the pure solvent
(Tf,solvent), cyclohexane, by recording its cooling curve i.e. its temperature as a function of time
as it cools down. By repeating the procedure for a solution containing w2 g of solute in w1 g of
the solvent you determine its freezing point (Tf,soln) and so obtain ∆Tf = Tf,solvent – Tf,soln. You
can then evaluate M2 using equation (3).
25
Schematic cooling curves of a pure solvent and a solution are shown in the following page. For
the pure solvent the freezing temperature is obvious, because the temperature remains constant
while it is freezing. The temperature then falls again when all the liquid has solidified. However,
for the solution the temperature does not remain constant during the freezing process. This is
because only the solvent freezes out and, as a result, the solution becomes progressively more
concentrated, so that the freezing temperature continues to decrease.
16 16
14 14
solvent solution
12 12
10 10
T/ C
T/ C
8
o
8
o
6 6
4 Tf 4 Tf
2 2
0 0
0 1 2 3 4 0 1 2 3 4
t/min t/min
Locate the temperatures when the solvent starts to freeze as indicated in these diagrams.
1. Cyclohexane is flammable. No open flames are allowed during the experiment.
2. Never pipette by mouth, always use a rubber suction bulb.
3. Dispose of all solutions in the flammable liquid residue bottle provided.
26
1. The apparatus consists of a freezing tube which fits into a cooling vessel. This holds the
test liquid, a stirrer and a thermometer. The cooling vessel contains an ice-water freezing
mixture.
2. Additional equipment to be found in the appropriate locker: pipette and rubber pipette
filler, magnifying glass, stop clock, spatula, 50 ml beaker and filter paper.
Procedure
(i) The freezing temperature of cyclohexane.
1. Fill the outer cooling vessel with ice-water to produce a freezing mixture. (Use the
minimum amount of water to produce a slurry.)
2. Make sure that the freezing tube is clean and dry.
3. Pipette exactly 20 cm3 of cyclohexane into the freezing tube. Close it immediately by
replacing the bung fitted with the thermometer and stirrer. (This cuts down any evaporation
loss).
4. Stir the cyclohexane gently but constantly. This is critical if good results are to be obtained.
5. Record the temperature every 15 s until the cyclohexane is frozen. Using a magnifying
glass, you should be able to read the temperature to a precision of about 0.05 ˚C.
6. Remove the freezing tube from the cooling vessel and allow the cyclohexane to melt and
return to room temperature.
7. Replace the freezing tube containing the cyclohexane and repeat steps 4 to 6.
27
(ii) The freezing temperature of a solution of the unknown solute in cyclohexane.
1. Weigh out accurately ~ 0.35 g of solute on to filter paper. Note its number!
2. Tip the solute into the cyclohexane in the freezing tube and reweigh the filter paper to
obtain the weight of solute added (w2).
3. Stir until you obtain a complete solution. All of the solid, including any on the walls of the
apparatus, must be dissolved before measurements can begin.
4. Stir the solution gently but constantly and record the temperature at 15 s intervals until the
entire solution is frozen.
6. Remove the freezing tube from the cooling vessel and allow the solution to melt and return
to room temperature.
7. Replace and repeat steps 4 to 6.
Results
(i) Freezing temperature of cyclohexane.
Plot the data as temperature (y-axis) against time (x-axis) in order to obtain both cyclohexane
cooling curves. Find the freezing temperature of cyclohexane by extrapolating the horizontal
section of data to the y-axis. Calculate the average Tf,solvent of the two runs.
(ii) Freezing temperature of the solution.
Plot the solution cooling curves and find the freezing point by determining the temperature at
which the set of linear sloping data points begin (see diagram). Hence obtain ∆Tf for your solute.
Evaluate the mass (w1) of cyclohexane used given that its density is 0.779 g cm-3.
Kf for cyclohexane is 20.2 K kg mol-1. Evaluate the molar mass of the solute using equation (2).
Remember to quote the number of your unknown solute.
28
Experiment 3. Thermochemistry: Thermochemistry and Hess’s Law
Aim
The aim of this experiment is to determine the enthalpy change (∆H) for each of three reactions
and to test Hess's Law.
Introduction
The enthalpy change is the heat released or absorbed by a reaction, for example:
CH4 (g) + O2 (g) → CO2 (g) + 2 H2O(l) ∆H = -802 kJ (1)
If ∆H is negative heat is given out, i.e. the reaction is exothermic. This heat goes into the
surroundings whose temperature will rise. If a reaction absorbs heat (from its surroundings) then
∆H is positive and the reaction is endothermic. Then, if the heat is taken from the surroundings,
their temperature will fall.
If a reaction is carried out in a calorimeter and the change in temperature of the calorimeter plus
its contents are measure, the amount of heat given out or taken in may be calculated.
You will use a simple calorimeter made from expanded polystyrene (a polystyrene cup!). The
heat capacity of this calorimeter is 10 J K-1. The heat capacity of its contents is 4.18 × m J K-1
where m is the mass of the contents expressed in grams. If Ti is the temperature of the calorimeter
plus contents before reaction, and Tf is the temperature after reaction, then ∆H is given by:
∆H = - (10 + 4.18 × m ) ∆T J (2)
where ∆T = (Tf -Ti ). Notice the minus sign!
The three reactions that you will study are:
NaOH + HCl → NaCl + H2O ∆H1
NH3 + HCl → NH4Cl ∆H2
NaOH + NH4Cl → NaCl + NH3 + H2O ∆H3
29
1. The solutions of HCl, NaOH, and NH3 are toxic and corrosive. In particular, solutions of
HCl and NH3 can cause chemical burns and ruin your clothing.
2. In the event of spillage wash the contaminated area thoroughly with water and report the
incident to the lecturer in charge.
3. Dispose of all solutions in the aqueous residue bottle provided
Equipment to be found in the appropriate locker: thermometer (- 5 to 50oC) , 3 ¯ 50 ml

measuring cylinders, two nested polystyrene cups, magnifying glass, stop clock, graph
paper and ruler.
Procedure
1. Put 50 cm3 of 2.0 M solution of HCl and 50 cm3 of 2.0 M solution of NaOH into two clean,
dry measuring cylinders. (In each case, this is 0.1 mole).
2. Measure the temperature of each solution using the same thermometer. However, rinse the
thermometer and dry it after the first measurement. The average temperature of the two
solutions is the initial temperature, Ti.
3. Add the HCl to the calorimeter, then add the NaOH and immediately place the top on the
calorimeter and gently mix for 30 s.
4. Record the temperature of the calorimeter contents to the nearest 0.05 °C after the 30 s and
every 30 s thereafter for 5 min.
5. Plot the temperature against the time. Use a ruler to extrapolate your results backwards, as
shown in Figure 1, to the time of mixing (t = 0). Record the extrapolated temperature, this
is Tf and it represents the highest temperature corresponding to the time at which the
solutions were mixed.
30
6. Repeat the above procedures using 2.0 M NH3 instead of NaOH.
7. Repeat again using 2.0 M NH4Cl and 2.0 M NaOH.
35
34
33
Tf = 31.1oC
32 Figure 1 – Determination of the
31
extrapolated temperature, Tf.
T/ oC
30
29
28
27
26
25
0 50 100 150 200 250 300 350
t/s
Results
1. From your time-temperature data, obtain Tf and hence ∆T for each reaction, then use
equation (2) to obtain ∆H for each reaction. To obtain m, assume the solutions have a
density of 1 g cm-3.
2. The heat changes you have measured relate to the reaction of 0.1 mole of each of the
reactants. Work out ∆H for 1 mol of reactants and report this in kJ mol-1 for each
reaction.
3. If the reaction for ∆H1 is combined with the reverse of that for ∆H2, then the reaction
relating to ∆H3 is obtained. It follows from Hess's Law that:
∆H3 = ∆H1 - ∆H2 (3)
4. Compare your experimental value of ∆H3 with that calculated from equation (3). Is
Hess’s law valid?
31
Experiment 4. Chemical Kinetics: The Iodine Clock
Aim
The aim of this experiment is to determine a reaction rate expression using an initial rate method.
Introduction
The rate of a reaction is determined by following the rate at which one of the products is formed
or the rate at which one of the reactants is consumed. The rate of a reaction depends on the
concentration of reactants. The dependence of the rate on the concentration of the reactants gives
the rate expression which has the following general form:
rate of reaction = k [A]m [B]n (1)
where m is the reaction order in A and n the reaction order in B. k is the rate constant and is
characteristic of a particular reaction at a given temperature.
In this experiment you study the rate of the reaction between hydrogen peroxide and acidified
potassium iodide.
H2O2 + 2 H+ + 2 I- → 2 H2O + I2 (2)
where
rate of reaction = k [H2O2]m [I-]n (3)
The reaction is carried out in the presence of a small amount of sodium thiosulphate (Na2S2O3)
which immediately reduces the iodine produced to iodide ions.
2 Na2SO3 + I2 → 2 NaI + Na2S4O6 (4)
It follows that I2 is continuously removed until all the thiosulphate is used up. After that, free
iodine appears in solution and this is easily detected because it forms a blue colour in the
presence of starch.
The time taken for the iodine (i.e. the blue colour) to appear is inversely proportional to the rate
of the reaction. If the reaction is fast, then the time is short. That is:
rate of reaction ∝ 1/ time (5)
The colour change is dramatic and the times so reproducible that this reaction is called an iodine
clock reaction.
32
In this experiment, the values of m and n in the rate equation will be deduced using the initial
rate method in three related experiments.
Experiment 1 is the reference, rate = R1.
In Experiment 2, rate = R2, where the initial concentration of H2O2 is twice that in Experiment 1
but the concentration of I- is unchanged. If the reaction is of order m in H2O2, then
R2 = 2m R1 (6)
In Experiment 3, rate = R3, the initial concentration of I- is twice that in Experiment 1 but now
the concentration of H2O2 is unchanged, so
R3 = 2n R1 (7)
1. 0.5 M sulphuric acid is toxic and corrosive, and can cause chemical burns.
2. In the event of spillage, wash the contaminated area thoroughly with water and report the
3. Never pipette by mouth, pipette the starch solutions using a rubber suction bulb.
4. Dispose of all solutions in the aqueous residue bottle provided.
Equipment to be found in the appropriate locker: four 50 ml burettes, thermometer (- 10

to 110°C) , four large boiling tubes, two size 21 rubber rings, 1 ml graduated pipette, 5 ml
graduated pipette, rubber pipette filler, four 100 ml beakers, 4 small filter funnels.
33
Procedure
1. Fill each of 4 burettes with the KI, H2SO4, Na2S2O3 solutions and water.
2. Clean and dry three boiling tubes. Prepare the following solutions in these clean tubes.
Experiment 3 3 3 3
KI (0.1M)/ cm H2SO4 (0.5M)/ cm Na2S2O3 (0.01M)/ cm H2O/ cm
1 10.0 20.0 5.0 12.0

2 10.0 20.0 5.0 10.0
3 20.0 20.0 5.0 2.0
3. Pipette 1 cm3 of starch solution into each tube and shake well.
4. Measure out 2 cm3 of H2O2 in a graduate pipette as accurately as possible.
5. To the mixture for Experiment 1, quickly add the H2O2 and start the stop-clock. Quickly
insert a rubber bung in the boiling tube and shake vigorously for 5 seconds to ensure a
completely homogeneous solution.
6. Record the exact time at which the blue colour appears. Be alert - the colour appears
suddenly throughout the solution. (If it does not, you have not mixed the solution
thoroughly enough)
7. Record the temperature of the solution.
8. Repeat steps 5 to 7 for Experiment 2, this time using 4 cm3 of H2O2.
9. Repeat steps 5 to 7 for Experiment 3, this time again using 2 cm3 of H2O2.
10. Wash, rinse and dry the boiling tubes and rubber stoppers.
11. Repeat steps 2 to 9 to obtain concordant results (that is times for each experiment which do
not differ by more than 10 seconds).
Note that the total volume for each experiment is constant and equal to 50 cm3. This
ensures that doubling the volume of a reagent doubles its concentration.
34
Results
Evaluate the average time, in seconds, for the starch colour to appear in each of the experiments.
Calculate the inverse (1/time) times, these are proportional to the reaction rates R1, R2 and R3.
Compare the 1/time values for experiments 1,2 and 3 and hence, using expressions (6) and (7),
evaluate m and n for this reaction.
Write down the particular form of the rate expression for this reaction.
35
Experiment 5. Equilibrium Constant: Determination of an Equilibrium

Constant
Aim
The aim of this experiment is to evaluate the equilibrium constant of a chemical reaction.
Introduction
All chemical reactions proceed until a state of equilibrium has been reached. Thereafter the
concentrations of reactants in the reaction mixture do not change with time. For the following
general reaction:
aA + bB → cC + dD (1)
at equilibrium
Kc =
[C ] [D ]
c d
(2)
[A]a [B ]b
Kc is the equilibrium constant, and the concentrations refer to those in the equilibrium mixture.
In this experiment, you will determine the equilibrium constant for the formation of the
thiocyano iron III complex ion. This ion is blood-red in colour and is the only coloured species
present in the equilibrium mixture. The net ionic equation that describes the reaction is
Fe3+ + SCN- ⇔ Fe(SCN)2+ (3)
with
Kc =
[Fe(SCN ) ] 2+
[Fe ][SCN ]
3+ −
(4)
To find Kc it is necessary to determine the molar concentrations of Fe3+, SCN- and Fe(SCN)2+ at
equilibrium.
By preparing a standard solution in which the concentration of the coloured complex ion
Fe(SCN)2+ is known, you can estimate the Fe(SCN)2+ concentration in a series of other solutions
by comparing their colour with that of the standard solution. The eye is surprisingly sensitive to
colour changes and, by careful observation, you can estimate concentrations quite accurately.
Colour comparison is done by viewing a test-tube containing the solution of unknown
36
concentration alongside an identical test-tube which contains the standard solution of complex
ion.
When the tubes are viewed vertically downwards the standard solution should be the more
intense in colour. The colour intensities are matched by gradual removal of some of the standard
solution. The concentration of complex ion in the unknown solution can be then evaluated from
the relationship
[ Fe( SCN ) 2+ ]unknown depth of s tan dard solution
= (5)
[ Fe( SCN ) 2+ ] s tan dard depth of unknown solution
1. 1 M nitric acid is toxic and corrosive, and can cause chemical burns. Never pipette by
mouth, always use a rubber suction bulb
3. Dispose of all solutions in the aqueous residue bottle provided
Equipment to be found in the appropriate locker: six test tubes, test tube rack, two 25 ml
burettes, glass Pasteur pipettes, rubber pipette bulb, disposable pipettes, 3 ¯ 100 ml
beakers, and ruler.
37
Procedure
(i) Preparation of the standard solution.
1. Pipette 10 cm3 of 0.20 M Fe(NO3)3 in 1 M HNO3 into a clean, dry test tube. Add exactly 2
cm3 of 0.0020 M NaSCN from a burette following by 8 cm3 of deionised water from a
burette.
2. Mix this solution thoroughly with a clean Pasteur pipette. In this solution, the concentration
of Fe3+ is very much greater than that of SCN-. Consequently, formation of Fe(SCN)2+ is
driven to the right of reaction (3), essentially to completion (Remember Le Chatelier’s
principle). That means that you may assume that all the SCN- is converted to Fe(SCN)2+
and so [Fe(SCN)2+] equals the initial molarity of SCN-.
Note, although you used SCN- = 2.0 x10-3 M, 2 cm3 of this was diluted to 20 cm3 so that
actual molarity of SCN- = [Fe(SCN)2+] = 2.0 x10-4 M. This is your standard solution.
(ii) Determination of the equilibrium constant, Kc.
1. Label five clean, dry test tubes 1 to 5.
2. Charge a burette with 0.0020 M Fe(NO3)3 in 1 M HNO3.
3. Add exactly 5.0 cm3 of the Fe(NO3)3 solution to each of the five test tubes.
4. Charge a second burette with 0.002 M NaSCN and add exactly 1.0, 2.0, 3.0, 4.0, and 5.0
cm3 of this solution to tubes 1 to 5.
5. Empty and thoroughly clean the burette containing the Fe(NO3)3 solution and then refill the
burette with deionised water.
6. Add 4.0 cm3 of water to tube 1; 3.0 cm3 to tube 2; 2.0 cm3 to tube 3; 1.0 cm3 to tube 4. No
water is added to tube 5.
7. Mix each solution thoroughly with a clean Pasteur pipette. The solution compositions are
summarized in the following table. In all cases the total volume is equal to 10 cm3.
38
Test tube 3 3 3
0.0020 M Fe(NO3)3 /cm 0.0020 M NaSCN /cm H2O /cm
1 5.0 1.0 4.0
2 5.0 2.0 3.0
3 5.0 3.0 2.0
4 5.0 4.0 1.0
5 5.0 5.0 0.0
8. Place test tube 5 next to the test tube containing the standard solution. Look down both
tubes towards a well illuminated piece of white paper as the background. Adjust the depth
of the standard solution by removing solution using a disposable pipette. Do not discard
any of the standard solution - you may need to return some solution if you overshoot in the
removal of solution. When the intensities of the colours in the two tubes match, measure
the depth of each solution with a ruler. This gives x, the concentration (in mol L-1) of
coloured complex in the equilibrium mixture
x = 2.0x10-4 (depth of standard solution)/(depth of unknown solution)
9 Repeat the procedure for matching of colour intensities of tubes 4, 3, 2 and 1 with the
standard solution.
Results
The equilibrium constant is calculated as follows. The reaction of interest is:
Fe3+ + SCN- ⇔ Fe(SCN)2+
a b 0 initial concentrations
a-x b-x x equilibrium concentrations
You have evaluated x for each of your solutions using the colour comparison. You know also a
and b for each solution, from the starting concentrations adjusted to take account of the dilution
factors.
39
Set up a table as follows:
tube a b x a-x b-x Kc

[Fe3+]in [SCN-]in [Fe(SCN)2+]eq [Fe3+]eq [SCN-]eq
-1 -1 -1 -1 -1
/ mol L / mol L / mol L / mol L / mol L
-3 -4
1 1x10 2x10
2
3
4
5
The starting molarities, i.e. the initial concentrations of Fe3+, [Fe3+]in, and SCN-, [SCN-]in, are
given for test tube 1. In this, 5 cm3 of the Fe3+ solution was made up to 10 cm3 and 1 cm3 of
SCN- solution was made up to 10 cm3. You must evaluate a and b for the other test tubes.
Complete the table. As long as the temperature remains constant Kc should be a constant.
From your five determinations, evaluate the average value for Kc and determine the precision of
your result by calculating the standard deviation as described in Appendix III. Quote your
answer ±σ, one standard deviation.
40
Experiment 6. Acids and Bases: Determination of Concentration using

Titration
Aim
The aim of this experiment is to measure the concentrations of acids and bases using the widely
used laboratory analytical technique of pH titration.
Introduction
The purpose of a titration is to determine the amount of a particular substance in a sample.
Frequently an indicator is employed to show when a stoichiometric amount of another substance
has been added from a burette. The same outcome may be achieved from a pH titration curve, but
this experimental procedure is much slower. However, a titration curve will allow an experienced
analyst to choose a suitable indicator allowing subsequent routine titrations of similar samples to
be done much more rapidly.
You will construct acid-base titration curves for
(a) strong acid—strong base (HCl - NaOH)

(b) weak acid—strong base (CH3CO2H - NaOH)
(c) strong acid—weak base (HCl - NH3)
(d) weak acid—weak base (CH3CO2H - NH3)
From your data you will be able to locate the equivalence points and thereby determine the
concentrations of the unknown solutions. You will also be asked to deduce what indicators are
suitable for subsequent titrations.
1. Aqueous solutions of HCl, NaOH, and NH3 are toxic and corrosive. Aqueous CH3OH is
corrosive. Never pipette by mouth, always use a rubber suction bulb.
41
1. The apparatus consists of a pH meter and electrode.
2. Additional equipment to be found in the appropriate locker: wash bottle containing

deionised water, 50 ml burette, 20 ml pipette and pipette bulb, four 100 ml beakers, filter
paper and graph paper.
Procedure
1. Follow the instructions given in Appendix IV for setting up the pH meter. Rinse the pH
electrode thoroughly in deionised water.
2. Pipette 20 cm3 of the HCl solution provided (it is about 0.1 mol L-1, but record its exact
molarity) into a beaker, place the electrode in the solution, swirl the solution and record the
pH. Keep the electrode in the solution and set up the burette so that it can deliver directly
into the solution.
3. Begin the titration by adding successive portions of ~1 cm3 of the NaOH solution and
record the burette reading and, after swirling the solution, record the pH after each addition.
There is no need to wait more than a few seconds between additions.
4. The pH will increase only slowly to begin with. When the increase in pH (that is the
difference between two successive pH values) gets to be more than about 0.3 pH units,
decrease the portions that you add to ~ 0.2 cm3. Once the equivalence point (end-point) has
been passed, the pH change after each addition will decrease. When the change is again ~
0.3 pH units, return to ~1 cm3 portions. Continue the titration until you are ~ 15 cm3
beyond the end-point. This completes titration (a).
5. Similarly obtain results for the titration of
(b) CH3CO2H (weak acid, pipette) against NaOH (strong base, burette)
(c) HC1 (strong acid, pipette) against NH3 (weak base, burette).
(d) CH3CO2H (pipette) against NH3 (burette).
Remember to rinse the glassware and pH electrode between titrations.
42
Results
From your tabulated pH data, construct plots of pH against volume (cm3) of base (NaOH or NH3)
added. Carefully draw smooth curves through the points.
The equivalence point is where the gradient of the titration curve is a maximum. Record this
point for each titration, along with your estimate of the uncertainty.
Knowing the concentration of HCl, calculate the concentrations (in mol L-1) of the NaOH,
CH3CO2H and NH3 from titrations (a), (b), and (c).
In an acid/base titration in which an indicator is used to identify the equivalence point, the
indicator must be one whose colour change happens at the pH of the equivalence point. By
referring to Appendix V, which shows the pH ranges in which common indicators change
colour, suggest indicators which would be suitable for titrations (a), (b) and (c).
43
Experiment 7. Spectroscopic Analysis of a Heavy Metal Contaminant:

Cobalt in Water.

Aim
The aim of this experiment is to verify the Beer-Lambert law and to use it to estimate the
concentration of Co2+ ions in a sample of water.
Introduction
Coloured substances absorb radiation that lies in the visible region of the spectrum (wavelengths
between 400 nm and 700 nm), thus a substance which appears blue to our eyes absorbs red light.
In this experiment, radiation of different wavelengths is passed through a sample and the
intensity of radiation transmitted (not absorbed) is recorded. Careful intensity measurements
using a spectrometer allow quantitative determination of the concentration of the absorbing
substance.
If the intensity of the light that enters a sample is Io and the intensity that emerges is I, then the
absorbance (A) is defined as:
Io
A = log (1)
I
It has been shown for many substances that absorbance and concentration are linearly related
A=k c (2)
where c is the solution concentration and k is a constant characteristic of the solute and the
wavelength. As A is dimensionless, the units of k are L mol-1. This is a statement of the Beer-
Lambert Law (often known simply as Beer’s Law).
In this experiment, you will test Beer's Law using a series of solutions of CoCl2 of known
concentration. You will then determine the concentration of a solution of CoC12.
44
1. Aqueous solutions of cobalt chloride are toxic and an irritant.
3. Never pipette by mouth, always use a rubber suction bulb.
1. Two type of spectrophotometers are available and instructions on how to operate these
are given in Appendix VI and VII for the Shimadzu UV mini-1240 and the Unicam
Heλios, respectively.
2. Additional equipment to be found in the appropriate locker: eight test tubes, 1 size 13
rubber bung, rubber pipette filler, test tube rack, plastic cuvettes, 25 ml burette, two 5 ml
graduate pipettes, two 100 ml beakers, filter paper and graph paper.
Procedure
The solutions to be studied are contained in small cells, which should be scrupulously clean.
Make sure that there are no air bubbles in the solutions to be analysed.
(i) Calibration data for the quantitative determination of CoC12.
1. Mark 7 dry test tubes with identification numbers from 1 to 7.
2. Using a pipette mix the following volumes of the CoCl2 solution provided (concentration
0.150 mol L-1) and water.
45
Test tube no. 3 3

CoCl2 solution / cm Water / cm
1 5.0 0
2 4.0 1.0
3 3.5 1.5
4 3.0 2.0
5 2.5 2.5
6 2.0 3.0
7 1.0 4.0
3. Thoroughly mix the contents of each test tube, but do not use your thumb as a stopper.
4. Fill a cell with solution 1 and measure its absorbance as a function of wavelength using the
spectrophotometer. Determine both λmax (the wavelength of the maximum absorbance) and
Amax (the absorbance at λmax). Evaluate Amax for the remaining solutions.
(ii) Determination of the concentration of CoC12 in an unknown solution
Cobalt occurs naturally in our environment, is essential for good health and is present in trace
amounts in soil and plants. The average concentration of cobalt in soils throughout the world is 8
parts per million (ppm), although cobalt concentrations in soils around old mine sites have been
reported as high as 6,450 ppm. Analysis for cobalt at this level can be achieved using the Beer’s
law data established above.
1. You have been given a solution containing an unknown concentration of CoC12. This
solution is too concentrated to be used directly and must be diluted. To establish the correct
dilution, first pipette 5 cm3 into a clean, dry test tube and dilute with water from a burette.
Record the volume of added water. Measure the absorbance of this solution at the
previously determined λmax. Continue diluting until the absorbance lies within the range of
your calibration data.
2. Your final result contains large experimental errors which have accrued during the several
dilutions. You must therefore prepare a new sample in one accurate dilution which is
equivalent to the overall dilution obtained in the previous set of trials. Establish what this is
and measure Amax of this diluted solution.
46
Results
(i) Determining calibration parameters for the quantitative determination of CoC12.
The equation for Beer’s law (2) is that of a straight line (y = m x) where y is the absorbance, x is
the concentration and the value of the slope m is k. Record your results in a table and plot Amax (y
axis) against CoCl2 concentration (x axis).
Draw the best straight line “by eye” through your data points and evaluate the slope. The line
should pass through the origin.
Also, using linear regression (see below) evaluate the slope. The value of k determined “by eye”
and from linear regression should be very similar. To estimate the uncertainty in the slope, draw
straight lines of maximum and minimum possible slope through your data points. Thus quote k
with its uncertainty.
(ii) Concentration of CoC12 in an unknown solution.
Evaluate the concentration of CoCl2 in the accurately diluted solution from its measured
absorbance and your k value. From your dilution factor calculate the concentration of the original
unknown solution. Quote the uncertainty in this final result.
Best Straight Line - Linear Regression Analysis
The gradient of the best straight line through the data points is given by
m=
∑ xy
∑x 2
The quantity ∑ xy is the sum of the product of each x (concentration) and its y (absorbance).
The quantity in the denominator ∑ x 2 is the sum of the squares of each x (concentration). The
slope computed using this equation is k in Beer's Law.
To get the best k value for your data points, compile a table of absorbance (A) against
concentration (c). Enter the product of each A and c in a third column and sum them. In the
fourth column enter the square each concentration, and sum these. Divide the first sum by the
second to obtain k.
47
Experiment 8. Effect of Pressure on Boiling Point/Boiling Point Elevation
by Dissolved Salts
Introduction
The relationship between the boiling point of a liquid and applied pressure is important in
chemical engineering operations such as distillation and evaporation. The dependence of boiling
point on pressure stems from the variation of the saturation vapour pressure of a liquid with
temperature, and this latter relationship has a wider significance in operations such as drying,
condensation and humidification.
The aim of this experiment is to show how the boiling point of a liquid (water) changes with
applied total pressure. Pressure is varied from a moderate vacuum up to atmospheric pressure.
Results should be plotted in the form of an Antoine plot, and checked against standard data.
As an extension, the elevation of boiling point caused by dissolved salts can be explored. This
effect is important in equipment such as evaporators and distillation reboilers.
N.B. FOR YOUR OWN SAFETY, DO NOT TAKE ANY READINGS AT ‘0’ ON THE
GAUGE (i.e. WITH THE VACUUM VALVE SHUT). AT THIS CONDITION YOU WILL
HAVE WATER BOILING AT 100oC, CREATING STEAM, IN A SEALED VESSEL. THERE
IS THEREFORE A POSSIBILITY OF THE VESSEL EXPLODING DUE TO EXCESS
PRESSURE.
WEAR SAFETY SPECTACLES AT ALL TIMES.
USE HEAT PROTECTION ON YOUR HANDS WHEN EMPTYING FLASKS OF HOT

WATER OR, PREFERABLY, LEAVE FOR THE EXPERIMENT SUPERVISOR TO
EMPTY.
Basic Theory
Vapour Pressure (P°) is the pressure exerted by a pure vapour above a pure liquid. It varies with
temperature. The curve of P° vs T can be termed the boiling point curve, the vapour pressure
curve or the saturation line. This dependence of vapour pressure on temperature can be
represented fairly accurately by the Antoine equation:-
48
B
ln P o = A −
T +C
where A,B and C are constant for a particular material

log can be either natural log ( loge or ln) or log to the base ten (log10 or log).
Therefore to show that this equation is relevant to the experiment, a plot of ln(pressure applied)
vs 1/boiling point should give a straight line.
Evaluation of the constants is not necessary as comparisons between lines is all that is required.
The addition of salt to the water should cause an elevation of boiling point. Why?
As boiling point is a colligative property and is only dependent on molal concentration, any
change due to the salt will be constant at all pressures. Therefore a plot of ln(P) vs 1/T should be
parallel to the water only plot.
The elevation in boiling point caused by the salt can be predicted by the equation:-
Boiling Point Elevation = Molal Elevation Constant x Molality
where Molal Elev. Const. for water = 0.52

Molality = Moles of solute / Kg. of solvent
Procedure
1. Using 500 ml ordinary tap water measure the boiling point of the liquid at various
pressures (by applying vacuum to the vessel).
Notes:
At a steady vacuum measure the boiling point temperature when the mercury in the
thermometer stops rising.
Start at a high vacuum and work towards atmospheric pressure - high vacuum (low
pressure) means low boiling point. It is easier gradually to heat up the water as you
decrease the vacuum.
2. Repeat the above experiment this time using a solution of a known quantity of salt (NaCl)
dissolved in 500ml. tap water. Use a minimum of 30gm of salt.
49
Points for Discussion/Questions
1. You should find that the BP elev. found doing the experiment is approximately twice that
calculated from the equation. Why? (hint: NaCl is an ionic salt)
2. A plot of standard vapour pressure data (from literature) for water (ln(Po) vs 1/T) is
significantly different from that found from the experiment. Again Why?
3. The reaction A → B is carried out in a laboratory reactor. If the kinetics are second order,
the concentration of A should vary with time according to:
C Ao − C A
= k .t
C A .C Ao
While if the kinetics are first order, the variation of concentration with time should be:
⎛ CA ⎞
ln⎜⎜ o ⎟ = k ′.t
⎟
⎝ CA ⎠
Where CA = molar concentration (kmol/m3) of A at time, t (min)

CAo = initial concentration of A
k, k′ are reaction rate constants.
The following experimental data was obtained:
T (min) 0.5 1.0 1.5 2.0 3.0 5.0 10.0

CA (kmol/m3) 1.05 0.69 0.51 0.41 0.29 0.18 0.096
Plot the data in such a way as to test each of the proposed rate laws, determine CAo and
the reaction rate constant for the more likely rate law.
50
Experiment 9. Verification of Boyle’s Law and the determination of the
molar volume of air at S.T.P.
Introduction
p v = constant
Boyle’s Law is a special case of the Ideal Gas Law, resulting from the application of an
isothermal compression or expansion process to an ideal gas system. At low temperatures and
pressures air will follow this ideal behaviour quite closely.
This experiment will enable you to verify Boyle’s Law at room temperature for air. Further
calculation will enable you also to determine the molar volume of air at S.T.P. (Standard
Temperature & Pressure, i.e. 0oc and 760mm Hg)
Method
Obtain a relationship between the volume measured on the syringe and the applied absolute
pressure using the apparatus provided. Pay particular attention to the repeatability of the results,
and look out for possible hysteresis effects in the apparatus.
Treatment of Results
When the syringe reads zero, the gas within the system will still occupy a volume (Bourdon
gauge + connecting tube).
pv=nRT
p (vm + vs) = n R T
Therefore:-
1/p = (vm / n R T) + (vs / n R T)
where vm = measured volume

vs = dead space volume
n = no. of moles of air in the system
R = Universal Gas Constant
T = Absolute temperature
51
Plotting 1/p vs vm gives a straight line of slope 1/nRT and intercept vs/nRT so that n can be found
from the slope and vs from the intercept.
Points to consider/Questions
1. Is p x v constant? If not, is it constant within experimental error? What are your error limits?
2. Molar volume, (vs + vm)/n = v at the experiment’s value of T and p. (Make sure you note the
room temperature and atmospheric pressure on the day.)
Therefore v at S.T.P. can be determined from this. Note: - STP and NTP are not the same.
Can you say what the difference is?
3. Whatever form the molar volume is quoted in the literature that you look at (i.e. at NTP or
STP), ensure that you convert your experimental value to the same form for comparison.
4. (i) List the potential sources of random and systematic errors in the following measuring
operations.
a. Measurement of liquid volume using a pipette.

b. Measurement of 100 g mass using (i) a beam balance (ii) an electronic balance.
(ii)Calculate the answers to the following expressions to the correct number of significant
figures.
a. 3.71 +15.6 – 0.006

b. 21.45 + 5.11 + 7.279
c. 293K x 8.314 kJ/kmol.K
5. BE AWARE AT ALL TIMES OF THE MAGNITUDE OF ERRORS DURING

MEASUREMENTS. CHECK ANY UNCERTAIN MEASUREMENTS TO DETERMINE
CONSISTENCY.
52
Experiment 10. Flash Point using the PenskyMartens Apparatus
SAFETY NOTES
1. Be Careful! You are using a naked flame in conjunction with flammable liquids.
2. Hot oil and water is a dangerous mixture - Dispose of tested solutions into the beaker
provided; when cool, decant into the marked waste bottle. DO NOT USE THE SINK.
3. Wear safety spectacles at all times.
4. Because of the use of hazardous chemicals, please read and comply with the COSHH ‘risk
assessment’ compiled for this experiment BEFORE starting any experimental work.
5. On completion of the experiment, please leave the apparatus in a clean, tidy and safe
condition.
Method
1. Various mixtures of n-heptane / liquid paraffin are provided - concentrations varying from
0.5cc n-heptane to 2.5cc n-heptane in 100cc liquid paraffin. For calculation purposes,
liquid paraffin can be treated as C11H24.
2. Thoroughly clean and dry all parts of the cup and its accessories before starting the test.
Take care to remove all solvent used in this cleaning.
3. Fill the cup with the n-heptane / liquid paraffin mixture up to the level indicated by the
marked line.
4. Place the cup in the apparatus and fit the lid (ensuring correct location). Insert the
appropriate thermometer. TAKE CARE WITH THE THERMOMETER - THIS IS A
SPECIAL AND IS EXPENSIVE AND DIFFICULT TO REPLACE.
5. Light the test flame and adjust to the size of a bead 0.16ins. (4mm) in diameter - the size of
the steel ball on the apparatus.
6. Light the Bunsen and control the heating to such a rate that the temperature recorded by the
thermometer increases not less than 9° nor more than 11°F /minute (5 to 6°C/min.). Turn
the stirrer at a rate of 1-2 revs/sec while heating.
7. Apply the test-flame at each temperature reading which is a multiple of 2°F (1°C) up to
230°F (110°C). For the temperature range above 230°F apply the flame every 5°F (2°C).
Make the first application at a temperature at least 30°F (18°C) below the flash
temperature. The test-flame should be lowered in 0.5 sec., left in its lowered position for 1
sec. and quickly raised. Stirring should be discontinued during application of the test-
flame.
8. Read the flash point as the temperature shown on the thermometer at the time of the flame
application that first causes a distinct flash in the cup. Do not confuse the true flash point
with the bluish halo, which sometimes surrounds the test flame in the preceding
applications.
53
Theoretical Model to be tested by the experiment
The following theory should establish how the flash point of a mixture of two liquids (one
relatively volatile, the other relatively non-volatile) varies with the mixture composition. You are
going to test this with your experimental data.
Let A be the more volatile (flammable) component

and B the less volatile (non-flammable) component.
The flammability of the vapour / air mixture above the liquid will be dominated by the
concentration of A in the vapour. Assuming ideality, this concentration is defined as:-
PA
yA = ............................................................ (1)
PT
where yA = mole fraction of A in vapour

PA = partial pressure of A in vapour
PT = total pressure of the system
Again assuming ideality, Raoult’s Law states that:-
PA = PAo . x A ........................................................... (2)
where xA = mole fraction of A in liquid

PoA = saturation vapour pressure of pure A
Combining (1) and (2) gives:-
x A . PAo
yA = .......................................................... (3)
PT
The Antoine equation is defined as:-
( )
ln PAo = A −
B
T +C
.............................................. (4)
where T = temperature
and A, B & C are the Antoine constants for component A
54
Substituting (4) into (3) then gives:-
B
ln( y A ) = ln( x A ) + A − − ln( PT ) .................. (5)
T +C
Now suppose that the air / vapour mixture becomes flammable at a critical vapour concentration
of A where yA = y*A. Then :-
( )
ln y *A = ln( x A ) + A −
B
TFP + C
− ln( PT ) ............... (6)
= constant at flash point
Rearranging this will give:-
ln( x A ) =
B
TFP + C
( )
+ ln y *A + ln( PT ) − A ............... (7)
which simplifies to:-
B
ln( x A ) = + K ........................................... (8)
TFP + C
where TFP = flash point temperature

K = constant
This theory can be tested by:
a) Substitution - using equation (8) and values from literature1,2 for the constants B and C,
substitute in each of your experimental data pairs (xA , TFP). Is K constant?
b) Graph - equation (8) suggests that a plot of ln(xA) against 1/(TFP+C) will give a straight
line of slope B. Again using literature data1,2 for C , this trend can be tested and an
experimental value for B determined. How does this compare to the published value?
i.e. different temperature units &/or logs. (°C or K or °F - log10 or loge).
55
Points to consider/Questions
1. As well as comparing the experimental and theoretical model, can you give an application
for the use of flash point?
2. We suspect that the following data follow the relationship:
y = a.xb
By plotting on log/log graph paper, verify the relationship and determine values of the
constants a and b, for the following two data sets.
x 1 2 3
y 1 4 9
x 1 2 5 10 20 50
y 0.5 1.41 5.59 15.81 44.72 176.8
References
1. R. M. Felder and R. W. Rousseau, Elementary Principles of Chemical Processes, 3rd Edn.,

John Wiley & Sons, 1999.
2. R. K. Sinnott and G. Towler, Chemical Engineering Design, SI edition, 5th Edn.

Butterworth Heinemann, 2009 (previously published as Coulson & Richardson’s Chemical
Engineering, Vol. 6).
NOTE: Check the definition of the Antoine equation in the literature you use, different units are
used in the different sources.
56
Experiment 11. Determination of the Thermal Properties of Water
Introduction
The thermal properties of water such as the latent heats of fusion and vaporisation, as well as the
specific heat capacity, can be obtained by subjecting a water system to a process of heating.
Since the operation is carried out at constant pressure, then the total heat (thermal energy) input
can be equated to the enthalpy change of the system and latent heats become the enthalpies of
fusion,∆hf, and vaporisation, ∆hv.
These are usually expressed per unit mass or mole of the system, and the heat input, or enthalpy
change itself, can in general be alternatively expressed in an intensive way.
Procedure (part 1)
1. Fill the beaker provided with ice up to the 800 ml mark and note the mass of ice used.
2. Add a known weight of water to fill the voids. (note its temperature before adding)
3. Submerge the heater (take care not to burn it out! SEE SAFETY NOTE).
4. Switch on the heater and start the stop-clock.
5. Keeping the mixture stirred (as far as possible), measure the temperature at regular
intervals, and note when all the ice has melted.
6. Continue heating and note the temperature as a function of time, until room temperature is
reached. Switch off the heater.
Note: Throughout the experiment carry out spot checks on the power consumption as given by
the electrical power meter, particularly noting the start and finish readings on the meter.
Procedure (part 2)
1. Check the mass of water in the beaker and top up to 800 ml if required (note the final
mass).
2. Place the beaker on the top-pan balance and immerse the heater, ensuring that the element
is covered with water.
3. Switch on the heater. Check the mass of water during heating, thus keeping an eye on any
evaporative losses. Note the temperature and power as a function of time and continue
heating until the water begins to boil.
57
4. Reset the stop-clock.

5. Note the time and power that it takes to evaporate a known mass of water, say 10-20 g.
Repeat this several times to measure the evaporation rate and the energy required to
achieve vaporisation.
TAKE CARE NOT TO DAMAGE THE HEATER, REFER TO THE SAFETY NOTES
SUPPLIED.
Energy balance on the ice/water system.
Assuming no heat gained from or lost to the surroundings.
Energy required to melt the ice = Energy from the water added + Energy from the immersion
heater
Energy required to melt the ice = M Cp ∆T + Heating power * time to melt all the ice.
Cp = The specific heat capacity of the water (energy/mass °C)

M = The mass of water added
∆T = (Temperature of water added - Temperature of ice/water mixture)
--------------
From an Energy vs Temperature graph, the Cp can be determined. The energy required to raise 1
unit of mass of water by one C degree is the slope , d (energy ) dT per unit mass of the system.
Energy = Heater power * time (or Total Energy used)
The appropriate portion of the graph could therefore be drawn as an Energy vs Temperature plot
(temp. on the x-axis for convenience) and Cp obtained directly from the slope. (i.e. use a temp.
range before evaporation is becoming significant).
--------------
58
Energy to melt the ice = ∆hf * Mass of ice used
∆hf = Latent heat of fusion of ice
similarly
Heater power * time to restore balance = ∆hv * Mass of water evaporated
∆hv = Latent heat of vaporisation of water.
Additional Question
The following expression is used to calculate the instantaneous discharge, Q, of a liquid with an
elevation, h, through a small orifice of area, A.
Q = K.A(2.g.h)0.5
where K and g are constants.
Determine the expression for the maximum relative error in Q as a result of small errors in the
measured elevation of the liquid and area of the orifice.
BE AWARE AT ALL TIMES OF THE MAGNITUDE OF ERRORS DURING

MEASUREMENT. CHECK ANY UNCERTAIN MEASUREMENTS TO DETERMINE
CONSISTENCY
59
Experiment 12. Specific Volume/Density Changes of Water as a Function
of Temperature
Introduction
• Density is a measure of specific volume and vice versa.

• Different states of matter are affected, to a different degree, in density by temperature change.
• Pure water forms a single component system and therefore the specific volume, v = f(T,P)
say, since two degrees of freedom exist.
• At constant atmospheric pressure, v = f(T) only since one of the degrees of freedom has
been removed.
Method
1. Prepare a water system (approx. 800 ml.) at a temperature as close to 20°C as possible by
using tap water and ice. Use the hot plate provided to melt the ice if necessary, but stir well
before noting the temperature. (see operational notes later)
2. Use the hydrometer and the density bottle to obtain the density of the water. (Notes on how
to use density bottles are available in Appendix VIII.)
Throughout the experiment, heat losses will vary so that in certain cases it will be
necessary to measure the temperature before and after the density determination so that an
average value can be obtained.
3. Using the hot plate increase the temperature in steps of 5-10°C and determine the water
density by both means if possible as a function of temperature.
Proceed as far as you can to the limit of the instrument or until the water becomes too hot
to handle (i.e. not any more than 60°C.).
4. Obtain a water system whose temperature is exactly 20°C and check that the hydrometer
calibration is correct.
60
OPERATIONAL NOTES
1. Refer to the safety instructions provided.

2. Use the 250 ml. measuring cylinder for hydrometer measurements.
3. Density bottle measurements are best made as a comparison of density to a standard
system. Hence specific gravity is most often determined.
Plot your results, ρ vs T (independent variable). Extrapolate the graph to the boiling point. Plot
the density vs temperature values given in the Steam Tables (1) (table 11) on the same graph, and
do the same with data obtained from Perry (The Chemical Engineer’s Handbook). Extend the
graph into the vapour region according to Steam Table data (present this information as you think
fit. e.g. another graph, a change of scale, a logarithmic scale ?)
1. R. W. Haywood, Thermodynamic Tables in SI Units, 3rd Edn., Cambridge University Press,

1990. (The tables issued to first year students contain similar information and may be used
as an alternative).
BE AWARE AT ALL TIMES OF THE MAGNITUDE OF ERRORS DURING

MEASUREMENT. CHECK ANY UNCERTAIN MEASUREMENTS TO DETERMINE
CONSISTENCY
Additional Question
Determine the maximum absolute error in the density, ρ, with a calculated value of 988 kg/m3,
given relative errors in the measurements of the mass, m, and the volume, V, of ±0.005 and
±0.01 respectively.
ρ = m/V
61
62
Appendix I. Layout of Laboratory Reports
Your report should be written on A4 paper, one side only, and, in the first year, it should not be
in excess of 8-10 pages long (including Title and Contents pages). The text of the report should
be word-processed. However, it is acceptable to add special characters (e.g. π, ρ, µ, etc.),
equations and diagrams by hand if you are not familiar with these functions in a word processor.
The important thing for you to remember is who the readership of your report will be. Your
report will be read and assessed by lecturers, but it needs to be written so that someone having
the same background and knowledge as you can pick up your report, understand what you have
done, repeat what you have done and get the same outcome. If this can’t be done using the report
you submit, you won’t get a good mark!
Laboratory reports are normally written in a standard format with different aspects grouped under
appropriate sub-headings, e.g.
Title Page: This should precede the text of the report and contain the following information:
Title of Experiment (and reference number)

Author's Name and Group Number
Experiment carried out on - (date)
Report submitted on - (date)
Supervisor's Name – (the person who actually supervised the experiment you did)
Contents: A separate page giving page numbers of the report sections.
Synopsis: This is a brief résumé of the WHOLE report and, in general, is no more than half a
page summarising the objectives, mode of execution, results, if appropriate, and main
conclusions of the study, and is the last part written once the rest of the report has been
finished! Remember that this should be a brief stand-alone summary that could be understood by
a person who was not already familiar with the experiment.
Introduction: A clear concise statement of the problem or aim / objective of the experiment.
Theory: A brief statement of the basic background theory involved in the experiment. However,
more credit will be given for an ability to use this theory in discussing your results.
62
63
Experimental Technique: A clear and concise account of what was actually done, with line
diagram and / or flow scheme. One point that should always be remembered when writing this
section is:
“Would I be able to carry out this experiment from what I have written?”
If the answer is no, then a better description is required. Also remember that you cannot assume
that a reader has prior knowledge of what you did or of the apparatus that you used. You need to
explain to him/her.
Results - Experimental and Derived: All experimental readings should be given in the report,
in tabular form with a title, as should any derived results. Any graphs should also be properly
labelled and have a title. Should there be complex calculations you should give a sample
calculation, however put it in an appendix at the end of the report. Similarly if there are a large
number of tables, graphs, etc., it is usual to put all these in appendices at the end of the report
with only the final derived results left in the text of the report. The tables, graphs, etc. can
then be referred to in the text as required.
Discussion of Results: This is an interpretation and explanation of the experimental results

taking account of the relevant theory. There should also be an appreciation of possible errors that
might have been present and their potential effects on the results.
Note: This is probably the most important section of the report, where you interpret and explain
your experimental results for the reader. Therefore you should be thinking clearly and carefully
before you write. It is not merely a repeat of the results found.
You will find questions at the end of some of the experiments. These should be answered fully,
referring to any relevant theory. Where present, these will be a help to form your discussion.
Conclusions: Here you summarise any conclusions that you have arrived at during your
discussion. These should be related to the stated objective of the experiment.
References : A list of all books, journals, etc. that you have referred to in the text of the report in
the correct standard reference format. (a rule of thumb is:- Where did any theory you quote
come from?)
Finally - any graphs should be full page and titled so that they are capable of standing on their
own.
63
64
Appendix II. Location of Experiments.
Please note the experiments are distributed over 2 locations. Experiments numbered 1 to 7 are in
the William Perkin building lab WP 2.25 and experiments 8 to 12 are located in the James
Nasmyth building JN G46 (near the Stores at the north end of the Workshop area).
Experiment Title Bench
1 Determination of Molar Mass of a gas WP 225: A1

2 Molar Mass from freezing Point Depression WP 225: A2
3 Thermochemistry and Hess’s Law WP 225: B1
4 The Iodine Clock WP 225: B2
5 Determining an Equilibrium Constant WP 225: C1
6 Acid-Base Titration Curves WP 225: C2
7 Analysis using Beer’s Law WP 225: D1
8 Effect of Pressure on Boiling Point JN G46
9 Verification of Boyle’s Law JN G46
10 Flash Point JN G46
11 Thermal Properties of Water JN G46
12 Specific Volume/Density Changes of Water JN G46
64
65
Appendix III. More Information on Significant Figures, Accuracy and

Errors.
Significant Figures
The phrase number of significant figures refers to the number of digits reported for the value
of a measured or calculated quantity, indicating the precision of the value. To count the
number of significant figures in a given quantity, we observe the following rules.
1 All digits are significant except zeros at the beginning of the number and possibly
terminal zeros (one or more zeros at the end of a number). Thus, 9.12 cm, 0.912 cm and
0.00912 cm all contain three significant figures.
2 Terminal zeros ending at the right of the decimal point are significant. Each of the
following has three significant figures: 9.00 cm, 9.10 cm, 90.0 cm.
3 Terminal zeros ending to the left of the decimal point may or may not be significant.
When a measurement is given as 900 cm, we do not know whether one, two or three
significant figures were intended unless it is explicitly stated. Any uncertainty can be
removed by expressing the measurement in scientific notation.
Scientific Notation
Scientific notation is the representation of a number in the form A x 10n, where A is a number
with a single non-zero digit to the left of the decimal point, and n is an integer, or whole number.
In scientific notation, the measurement 900 cm precise to two significant figures is written 9.0 x
102 cm. If precise to three significant figures, it is written 9.00 x 102 cm. Scientific notation is
also convenient for expressing very large or very small quantities. It is much easier (and it
simplifies calculations) to write the speed of light at 3.00 x 108 (rather than as 300,000,000)
metre per second.
Significant Figures in Calculations
Measurements are often used in calculations. How do we report the significant figures in a
calculation? Suppose we have measured the solubility of a material. We find that 0.0634 g of
the substance dissolves in 25.31 g of water. The amount dissolving in 100.0 g is:-
(0.0634 g material) x (100.0 g water)/(25.31 g water)
Performing the arithmetic on a pocket calculator, we get 0.2504938 for the numerical part of the
answer (0.0634 x 100.0 / 25.31). But it would be incorrect to give this number as the final
answer, because it is much more precise than the other numbers in the calculation.
Multiplying or dividing measured quantities, then we should give the same number of decimal
places in the answer as there are in the measurement with the least number of decimal places. In
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the preceding calculation, 0.0634 g has the least number of significant figures (three). Hence the
answer should be reported to three significant figures, that is. 0.250 g.
Addition or subtraction of measured quantities, then we should give the same number of
decimal places in the answer as there are in the measurement with the least number of decimal
places. Suppose we wish to add 184.2 g and 2.324 g. On a calculator, we find that 184.2 + 2.324
= 186.524. But because the quantity 184.2 g has the least number of decimal places, one,
whereas 2.324 g has three, the answer is 186.5 g
Note that any number whose value is known exactly does not affect the number of significant
figures in a result. For example, there are 12 inches in 1 foot. The number 12 is known exactly,
so (12 inches/foot) x (3.16 feet) = 37.9 inches. The number of significant figures is determined
by 3.16, not 12.
Rounding
In reporting the solubility of our substance in 100.0 g of water as 0.250 g, we rounded the
number we read off the calculator (0.2504938). Rounding is the procedure of dropping non-
significant digits in a calculation result and adjusting the last digit reported. The general
procedure is as follows. Look at the leftmost digit to be dropped.
1. If this digit is greater than 5, or is 5 followed by non-zeros, add 1 to the last digit to be
retained and drop all digits farther to the right. Thus rounding 1.2151 to three significant
figures gives 1.22
2. If this digit is less than 5, simply drop it and all digits farther to the right. Rounding
1.2143 to three significant figures gives 1.21.
3. If this digit is simply 5 or 5 followed by zeros, and if the last digit to be retained is even,
just drop the 5 and any zeros after it. If the last digit to be retained is odd, add 1 to it and
drop the 5 and any zeros after it. For example, rounding 1.225, 1.22500 and 1.21500 to
three significant figures gives 1.22 in each case.
In doing a calculation of two or more steps, it is desirable to retain additional digits for
intermediate answers. This ensures that small errors from rounding do not appear in the final
result. If you use a calculator, you can simply enter numbers one after the other, performing each
arithmetic operation and rounding just the final answer.
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Estimating Combined Errors
It is possible to estimate the maximum error in the value of a function that depends on one of
more direct measurements.
The two methods of doing this use either algebra or calculus.
ALGEBRAIC ESTIMATION OF COMBINED ERRORS
Derivation of the algebraic method is given by J. Topping, Errors of Observation and their
Treatment, Chapman & Hall, 1962
In summary, the maximum errors can be estimated for the following simple types of function as
follows.
Error in a Sum or Difference
ε max= Σε i
Where εmax = maximum absolute error in the sum or difference

εi = absolute error in each individual measured quantity
Example 1 Two lengths are measured as:
L1 = 0.100 ± 0.001 m
L2 = 0.090 ± 0.001 m
Determine the maximum absolute error and maximum relative error in the values of
a L1 + L2 and b L1 – L2
a Absolute error of the sum

ε1 + ε2 = 0.001 + 0.001 = ± 0.002 m
The relative error is therefore:

ε 1 + ε 2 0.002
= = ±0.01 (or 1%)
L1 + L2 0.190
b Absolute error of the difference is the same as for the sum i.e. 0.002 m
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The relative error is therefore:

ε 1 + ε 2 0.002
= = ±0.2 (or 20%)
L1 − L2 0.010
Note that in determining the maximum (i.e. worst case) error in the value of the function, the
signs of the individual errors are selected so that their values are always additive. This even
applies when the individual terms to which they are attached (e.g. L1 and L2) are subtracted.
Error in a Product or a Quotient
f max = Σf i
Where fmax = maximum relative error in product or quotient

Fi = relative error in each individually measured quantity
Example 2 A quantity is calculated from the equation:
a 2b
y=
c
If the values of the right-hand terms are obtained from direct measurements with the following
percentage errors: a ± 0.1%, b ± 0.5%, c ± 0.3%, determine (a) the maximum relative error in y
and (b) the maximum error in y when y = 5.
(a) Maximum combined relative error in y:
f1 + f 2 + f 3 = 2 × 0.001 + 0.005 + 0.003 = ±0.01 ( or 1%)
(b) Maximum combined absolute error when y = 5:
y ( f1 + f 2 + f 3 ) = 5 × 0.01 = ±0.05
ESTIMATION OF COMBINED ERRORS USING CALCULUS
Differential calculus is the most convenient method of estimating consequential and combined
errors in more complicated functions.
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Given that x is a measured quantity and y is the value of a function that depends on it, such that:
y = f (x )
Then a small error δx in x produces a consequential error δy in y.
Assuming that δx is sufficiently small
δy dy
=
δx dx
δx Limit → 0
And the absolute error in y is given by:
dy
δy = δx
dx
The relative error in y is then given by dividing the derivative by the function f(x)
δy 1 dy
= δx
y f ( x ) dx
πx 2
Example 3 y is the area of a circle of diameter x, so that y =
4
The derived function is
dy πx δy
= =
dx 2 δx
Thus the absolute error δy in y that occurs as a consequence of the error δx in x is:
πx
δy = δx
2
Dividing the derived function by f(x) gives the relative error in y:
δy 4πx δx
= δx = 2
y 2πx 2
x
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The relative error in the area y is therefore approximately twice the relative error in the diameter
x.
Note that the same answer is arrived at using the algebraic method:
δy δx
If f max = and f = then f max = 2 f
y x
When the function contains two or more directly measured quantities, the PRINCIPLE OF
SUPERPOSITION OF ERRORS must be used. This means:
∂y ∂y ∂y
δy = δa + δb + δc + ....
∂a ∂b ∂c
∂y
The term is the partial differential coefficient denoting the result of differentiating y with
∂a
respect to the variable a with all others treated as constants. Thus
∂y
δa
∂a
Is the error in y due to the error δa in a alone. As for the algebraic method it is pessimistically
assumed that the individual errors always combine so as to produce the maximum possible error
in y. The signs of δa, δb, δc, etc. are therefore chosen so that the values of the partial differential
error terms always add.
Example 4 If y is the volume of a cylinder of diameter x and length L, so that:
π
y= x2L
4
The partial differential coefficients are:
∂y π ∂y π 2
= xL and = x
∂x 2 ∂L 4
Applying the principle of supposition of errors, the absolute error in y is:
πxL πx 2
δy = δx + δL
2 4
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And the relative error is:
δy 4πxL 4πx 2 δx δL
= δx + δL = 2 +
y 2πx L
2
4πx L
2
x L
The algebraic method, as applied to the combined relative error in a product, gives the same
result:
⎛ δx ⎞ δL
if f1 = 2⎜ ⎟ and f 2 =
⎝ x⎠ L
⎛ δx ⎞ δL
Then f max = 2⎜ ⎟ +
⎝ x⎠ L
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72
Appendix IV. Calibration of a pH meter
1. Immerse the pH electrode and the temperature/ ATC probe in the pH 7 (GREEN) buffer
solution
2. Allow the displays to stabilise and then press the CAL keypad. The main display will
momentarily read CAL1 and will be set to the temperature adjusted value of the buffer
solution. The CAL indicator will be flashing to remind you that the second part of the
calibration is still to be carried out.
3. Remove the electrodes from the pH 7 (GREEN) buffer solution and rinse with deionised
water.
4. Immerse the pH electrode and temperature/ATC probe in the pH 4 (ORANGE) buffer

solution.
5. Allow the displays to stabilise and then press the CAL keypad. The main display will
momentarily read CAL2 and will be set to the temperature adjusted value of the buffer
solution. The CAL indicator will stop flashing, indicating that the calibration is complete.
Note: Once the pH meter has been calibrated, no further calibration should be necessary
during your experiment.
6. Remove the electrodes from the buffer solution and rinse with deionised water.
7. The unit is now calibrated and the pH and temperature of your unknown samples may now
be measured.
Please leave the electrodes immersed in pH 4 (ORANGE) buffer solution after you have
completed your experiment.
72
pH range
0 – 1.6
1.2 – 2.8
Appendix V. Indicator Colours
3.0 – 4.6
73
3.2 – 4.4
4.8 – 6.0
8.3 – 10.0
5.0 – 8.0
10.1 – 12.0
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74
Appendix VI. Shimadzu UV mini1240 Spectrophotometer
The spectrophotometer will be switched on for you.
SET UP
Press 2 to select spectrum.

Press 1 to select ABS (Absorbance) then press enter.
Press 2 (λ range): Enter λ range 600 nm to 400 nm.
Press 3 (Rec. range): Enter 0.00 A to 1.00 A.
Press 4 (Scan speed): Select medium then press enter.
Press 5 (No. of scans): Select 1 then press enter.
Leave 6 (Display mode): on Sequential.
The instrument is now ready to record the absorbance, A from 400 – 600 nm.
The maximum absorbance should be less than 1.000.
PROCEDURE
1. Select a clean absorbance cell (cuvette). Make all your measurements in this cell.
2. Fill the cell to ¾ full with water and put it in the sample holder.
3. Press Base corr – This allows you to set a blank sample.
4. Now put your sample in the same cell.
5. Again, put the cell in the holder.
6. Press the start/stop key and measurement will begin. The spectrum is displayed on the
screen.
7. When the run is complete press Peak. Read off Amax and λmax
8. Press Return twice.
9. Repeat the same procedure from 4, for the rest of your solutions.
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Appendix VII. Unicam Heλios Spectrophotometer
The spectrophotometer will be switched on for you.
SET UP
First, check that the displayed parameters are:
*SCAN*
ID
MODE ABS
START 400.0 nm
STOP 600.0 nm
BANDWIDTH 2 nm
SPEED NORMAL
DATA INTERVAL 1.0 nm
PEAK TABLE PEAKS
GRAPH HIGH 1.000
GRAPH LOW 0.000
LAMP CHANGE 325 nm
USER CHEM
CELL PROG OFF
REF MODE OFF
These indicate that:

1. the instrument is set to record the absorbance, A from 400 - 600 nm.
2. measurements are made at intervals of 1.0 nm
3. Amax and λmax will be given
4. the maximum absorbance should be less than 1.000
PROCEDURE
1. Select a clean absorbance cell. Make all your measurements in this cell.
2. Fill the cell with water and put it in the appropriate sample holder.
3. Press ZERO BASE
4. Wait while the instrument scans a base-line. (This will be subtracted from subsequent
scans)
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5. Now, put your sample in the same sample cell.

6. Again, put the sample cell in the holder
7. Press RUN
8. The absorbance is displayed on the screen. (Notice that the peak is marked with a
vertical line).
9. When the run is complete, press VIEW RESULTS
10. Read off Amax and λmax
11. Press HOME followed by ENTER
12. Repeat the RUN procedure for each of your solutions.
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Appendix VIII. Density Bottle Principles
Density bottles are made to hold exactly 50 ml, 100

ml, etc. of liquid at a specified temperature.
At any other temperatures however this volume will

vary due to expansion / contraction effects.
The bottle is filled to the top, any excess liquid is

allowed to escape through the vent in the stopper
when the stopper is inserted into the bottle. The outside of the bottle and stopper are carefully
dried before weighing. The meniscus of the liquid being just below the top of the stopper.
Specific Gravity is the relative density of a substance compared to water at a specified

temperature.
ρ
SG =
( ρ H 2O ) T
The density of water is 1 gm/ml only at 4°C.
Hydrometers measure Specific Gravity and therefore must have a reference temperature
stated on them.
e.g. the laboratory hydrometers have a reference temperature of 20°C
ρ = SG × ( ρ H 2 O ) 20C
where SG = hydrometer reading
If a density bottle is to be used to measure the same specific gravity as the hydrometer, it
must also be referred to the same reference temperature (20°C in this case).
ρ = Mass of liquid in bottle

Bottle volume --- (not known exactly)
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So:-
mass
ρ vol. mass
SG = = =
( ρ H 2O ) 20C (massH 2O ) 20C (massH 2O ) 20C
vol.
The volume of the density bottle is eliminated and therefore need not be known at all.
--------------------------
The density of a solid can also be measured in a density bottle.
A density bottle is filled with water at room temperature (the

water temperature must be known)
The weight of water in the bottle in measured

(1)
A known weight of solid whose density is to be measured...

(2)
...is added to the density bottle so that some of the water is

displaced. The combined contents of the density bottle are then
weighted.
(3)
(4) = (3) - (2) is the weight of water remaining in the bottle
(5) = (1) - (4) is the weight of water displaced
If the density of the water at the water temperature ( ρ H 2 O ) T is known
Then
(5)
( ρ H 2O ) T is the volume of water displaced = Volume of solid added
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( 2)
Therefore Solid Density =
(5)
( ρ H 2O ) T
79

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Schooll of Enggineeringg & Phyysical Sciences

Chhemicaal Enggineeering Labor

Acaddemicc Yeaar 20112/13

Experiment 11. Determination of the Thermal Properties of Water 57

This is what you should do:

DEMONSTRATORS AND MEMBERS OF STAFF ARE HERE TO HELP YOU.

All glassware and equipment needed for experiments in WP 2.25 is to be found

(Note: This is a procedure you should be adopting as a general

8. Any defects in and / or breakage of equipment should be reported immediately to the

9. Disposal of glass, chemicals and solvents:

Moral of the situation? DON’T BE LATE!!!

4. Accuracy of the experimental data.

Precision and accuracy

Significant figures in calculations

In multiplication or division of measured quantities - give as many significant figures in the

(More information on this topic is available in Appendix III.)

Suppose measurements of ρ, g and h have given the following results:

ρ = (13.595 ± 0.001) g cm-3 = (1.3595 ± 0.001) 104 kg m-3

g = (9.811 ± 0.001) m s-2

P = 14.9920 x 103 N m-2

dP/P = dρ/ρ + dh/h + dg/g

= 0.0001/1.3595 + 0.0002/0.1124 + 0.001/9.811

∴ dP = 0.002 x 14.9920 x103 = 0.03 x 103

P = (14.99 ± 0.03) x 103 Nm-2

dρ/ρ = dM/M – dV/V

V = (5.01 ± 0.04) cm3

dρ/ρ = 0.001/0.245 – (-0.04)/5.01

dρ = 0.00059 = 0.059 x 10-2 g cm-3

ρ = (4.89 ± 0.06) x 10-2 g cm-3

The average value,

(2.0 + 2.1 + 2.1 + 2.0 + 2.0 + 1.8)/6 = 2.0

(0.0 + 0.1 + 0.1 + 0.0 + 0.0 – 0.2)/6 = 0

Power functions of the form:

are plotted on log-linear graph paper, a straight line results.

ny = log(ymax/ymin) and nx = log(xmax/xmin)

ny = log(ymax/ymin) = log (176.8/0.5) = 2.548 = 3 cycles on ordinate

For the power functions where y = axb:

The equation of the line is therefore

For exponential functions where y = aebx:

The more mathematical way,

Gradient = log y2 – log y1/ log x2 – log x1

e.g. equation is y = axb

If you take logs

Safety and Hazard Assessment

Equipment and Apparatus

2. Additional equipment to be found in the appropriate locker: 2 cm3 hypodermic syringe

Calculate the average value of M from your measurements.

Combining equations (1) and (2) gives:

Safety and Hazard Assessment

1. Cyclohexane is flammable. No open flames are allowed during the experiment.

2. Never pipette by mouth, always use a rubber suction bulb.

3. Dispose of all solutions in the flammable liquid residue bottle provided.

Equipment and Apparatus

(i) The freezing temperature of cyclohexane.

2. Make sure that the freezing tube is clean and dry.

(ii) The freezing temperature of a solution of the unknown solute in cyclohexane.

7. Replace and repeat steps 4 to 6.

(i) Freezing temperature of cyclohexane.

(ii) Freezing temperature of the solution.

CH4 (g) + O2 (g) → CO2 (g) + 2 H2O(l) ∆H = -802 kJ (1)

∆H = - (10 + 4.18 × m ) ∆T J (2)

where ∆T = (Tf -Ti ). Notice the minus sign!

The three reactions that you will study are:

NaOH + HCl → NaCl + H2O ∆H1