NOTICE TO ALL CHEMISTRY STUDENTS

All students working in the Chemistry undergraduate laboratories MUST WEAR INDIRECTLYVENTED CHEMICAL SPLASH SAFETY GOGGLES AT ALL TIMES.

All students must familiarize themselves with the safety rules pertaining to a particular experiment
(e.g. use fume hood, wear gloves, do not pipet by mouth, etc.).

STUDENTS WITH ANY KIND OF MEDICALLY RELATED CONDITIONS (e.g. seizures,

etc.) or who are pregnant must contact the course instructor for information regarding the advisability
of taking this lab course.

ANY STUDENT WHO NEGLECTS TO FOLLOW THE SPECIFIED, SAFE PROCEDURE

FOR CONDUCTING AN EXPERIMENT AS DESCRIBED IN THIS MANUAL, OR WHO
PERSISTS IN REFUSING TO FOLLOW THE NORMAL SAFETY RULES, WILL BE
ASKED TO LEAVE THE LABORATORY FOR THE REMAINDER OF THE
LABORATORY PERIOD.

TABLE OF CONTENTS

Introduction

Lecture and Test Schedule

Laboratory and Tutorial Schedule

Textbook Assignments (for practice)

Additional Problems - Unit 1 - Solution Concentrations (for practice)

Tutorial Assignments 1 - 5 (for credit)

Lecture Note Supplement - Unit 2 - Solution Equilibria

12

Marking Scheme

30

Policies Regarding Work Not Done or Submitted Late

30

General Laboratory Instructions

31

Materials

33

Safety

33

Laboratory Practice

34

The Laboratory Notebook

36

The Report

37

Laboratory Report Marking Scheme

39

Integrity and Ethics in the Laboratory

39

Experiments
1.

Separation of Metal Ions by Paper Chromatography

41

2.

Behaviour of Gases

53

3.

Analysis of Antacids by Acid-Base Titration

65

4.

Spectrophotometric Determination of the Formation Constant of a

Complex Ion

75

5.

Measurement of the Enthalpy of Reaction by Calorimetry

85

A.

Error Analysis

103

B.

Beer-Lambert Law

110

C.

Spectronic 20

Appendices

114

CHM 110H5F
Chemical Principles 1
2013 - 2014
http://www.utm.utoronto.ca/~w3chm140
Welcome to CHM110H. I hope that through this course you will come to appreciate chemistry as
an integral part of our culture. You should also become comfortable in dealing with a changing body
of knowledge through developing an appreciation of the processes of chemical research. I look
forward to meeting each of you, to advising on your programs in the sciences, and to mentoring you
as you progress towards your goals.
Instructor:

Lecture
Times:

Texts:

Judith Po
Room: 4048, Davis Building
Phone: (905) 828-3803
E-mail: preferrably via Virtual Office Hours on the course website listed
above or, if VOH is not available, at judith.poe@utoronto.ca
Office Hours: M, W 12:15-1:30p.m.

M, W, F
or
M, W, F

9-10

Room IB110

11-12

Room KN137

M.S. Silberberg, S. Lavieri and R. Venkataswaran, Chemistry: The

Molecular Nature of Matter and Change, Canadian Edition, McGraw-Hill
Ryerson (2013) - with Students Solutions Manual and Connect
CHM110H Course Manual - You must print this, put it in a binder and
bring it to each laboratory and tutorial class.

Other
Required
Materials:

1.
2.
3.
4.

indirectly-vented, chemical splash safety goggles

lab coat (100% cotton recommended)
disposable gloves and/or kitchen type gloves
non-programmable calculator (Note that the only calculators that
will be allowed in tests and exams are the following: TI-30XIIS
or CASIO fx-260 solar).

Lecture and Test Schedule 2013-2014

Starting
Date

Unit

Sept. 9
Sept. 11

Number
of
Lectures

Chapters

1
1

Topic
Introduction to the Course and its
Web Site

1 - 4 and 12.3-12.5

Matter, Reactions and Solution

Stoichiometry

Behaviour of Gases

Sept. 30

11

15 - 17

Equilibria

Oct. 30

5 and 18

Thermodynamics

19.1-19.6

Electrochemistry

.
Mid-term Tests:

Monday, October 7, 8:00-9:00 a.m. (no CHM110H lectures on this day)

Monday, November 4, 8:00-9:00a.m.(no CHM110H lectures on this day)
Students with another class at this time must inform the instructor by email of the course and the room in which it meets at least one week in
advance of the test. Those students only will be allowed to write the tests
from 9-10 a.m.

Final Exam:

Sometime in the period of December 9 - 20, time and place to be determined

Personal plans for this time period that interfere with your availability
to write a final exam are not considered legitimate excuses for missing
an exam. Therefore do not make any personal plans for this time period
until the exam schedule is published by the Registrars Office.

Laboratory and Tutorial Schedule 2013-2014

Week
beginning

L/T

Work to be Done

Sept. 9

Laboratory Safety, Exercises in the Use of

Laboratory Equipment

16

Assignment 1
Quiz 1

23

Exp. 1 - Separation of Metal Ions by Paper

Chromatography

30

Assignment 2
Quiz 2

Oct. 7

Exp. 2 - Behaviour of Gases

14

Assignment 3

21

Exp. 3 - Analysis of Antacids by Acid-Base

Titration

28

Assignment 4
Quiz 3

Nov. 4

Exp. 4 - Spectrophotometric Determination of

the Formation Constant of a Complex Ion

11

Assignment 5
Quiz 4

18

Quiz 5

25

Exp. 5 - Measurement of Enthalpy of Reaction

by Calorimetry

Work Due

A. 1
Exp. 1
A. 2
Exp. 2
A. 3
Exp. 3
A. 4
Exp. 4
A. 5
Exp. 5*

All lab reports and tutorial assignments must be submitted in hard copy.
* Note that lab reports are due in your tutorial class in the weeks noted in the schedule with
the exception of Exp. 5. All reports for Exp. 5 are due by 5:00p.m. on Wednesday, December
4.
.

Textbook Assignments
The following Chapters will be studied in the fall term:
Unit 1 - Stoichiometry - 1-4 and 12.3-12.5
Unit 2 - Equilibria - 15-17 (plus notes on pages 12-29 of this manual)
Unit 3 - Thermodynamics and Electrochemistry - 5, 18 and 19.1-19.6
The assigned problems are listed below. It is recommended that you focus on the problems
numbered in green whose answers are in Appendix D and whose complete solutions are in the
Student Solutions Manual. These problems will be discussed in your tutorials. These problems are
not to be handed in, however their content will be reflected in the quizzes.

UNIT 1
Chapters 1 - 4
all green problems
Chapter 12
problems 12.44 - 12.70 plus additional problems on page 5 of this manual

UNIT 2
Chapter 15 - 17
all green problems

UNIT 3
Chapter 5 and 18
all green problems
Chapter 19
green problems 1 - 81 and 121, 125, 137, 154

Additional Problems - Unit 1

Solution Concentrations
Consider each of the following aqueous solutions at 25oC.
1.

2.

3.

4.

98.0% w/w

= 1.842 g mL-1

Given:

H2SO4

Find:

molarity, molality and mole fraction of acid

Given:

Cr2(SO4)3

Find:

mole fraction, density and % w/w

Given:

H3PO4

Find:

molarity, molality and % w/w

Given:

C2H4(OH)2
ethylene glycol

Find:

molarity, % w/w and mole fraction of ethylene glycol

1.26 M

= 1.412 g mL-1

4.028 m

Answers
1.

18.4 M, 500 m, X = 0.900

2.

X = 0.0241, = 1.41 g mL-1, 35.0 % w/w

3.

57.8 m, 12.2 M, 85.0 % w/w

4.

3.299 M, 19.97 % w/w, X = 0.06756

1.37 m

Xacid = 0.510

= 1.024 g mL-1

Tutorial Assignments
General Instructions

Unlike the other assignments, tutorial assignments are to be handed in and will be marked. You
should attempt to do the assignment before the tutorial in which it will be considered. In the tutorial,
the TA will not tell you how to do the assignment. But he/she will guide you in an approach to the
assignment and will try to answer your questions while not telling you the solution. You will then
have an opportunity to revise and improve upon your initial work before handing in the assignment
the following week. To gain the most benefit from the tutorial and the opportunity to revise your
work, you must have come to the tutorial prepared, i.e. having already worked on the assignment.
Formatting:
1.

Do not include a cover page.

2.

The following information should appear cross the top of the first page:
name and student number, lab section number, TAs name, assignment number

3.

Use 1 inch margins, 1.5 line spacing and 12 point Times New Roman font (10 point for
references).

4.

Assignments must not exceed two pages in length, including any graphs, calculations and
references where appropriate.

5.

References should be given superscript numbers in the text and listed at the end of the
assignment.

Assignments are due in your laboratory or tutorial class in the weeks noted in the schedule on page
3 of this manual. The penalty for late assignments is 5% off of the assignment mark per calendar day
to a maximum of 7 days after which a mark of zero will be given.
Unlike experiments, quizzes and tests which can only be done on a particular day, assignments can
be done over a period of many days or weeks. Therefore medical or other excuses will not be
accepted as a reason for missing an assignment (excepting, of course, in the unfortunate circumstance
of a prolonged, serious illness).

Assignment 1

a.

A 1.00 g sample of enriched water, a mixture of H2O and D2O, reacted completely with Cl2
to give a mixture of HCl and DCl. The HCl and DCl were then dissolved in pure H2O to
make a 1.00 L solution. A 25.00 mL sample of the 1.00 L solution was reacted with excess
AgNO3 and 0.3800 g of an AgCl precipitate formed. What was the mass % of D2O in the
original sample of enriched water?
Atomic masses (g/mol): H = 1.0, D = 2.0, O = 16.0, Cl = 35.5, Ag = 107.9

b.

The mass % natural abundance of the isotopes H and D are 99.985 and 0.015 respectively.
The mass % natural abundance of the isotopes 16O, 17O and 18O are 99.759, 0.037 and 0.204
respectively. In a mass spectrometry experiment on naturally occurring water, at what m/
values would you expect to observe the three most abundant peaks for the molecular ions and
what would you expect to be their relative abundances?

c.

For questions a. and b. above, explain the process by which you arrived at a plausible solution.
In developing your answer, justify the steps you have undertaken (i.e., use analogies/examples
to support the choice of steps that you have undertaken in solving the two questions above).

Assignment 2

P (atm)
PV (L atm)

1.00000
22.2643

0.66667

0.50000

0.33333

22.3148

22.3397

22.3654

0.25000
22.3775

0.16667
22.3897

Data for PV as a function of P for 1 mol of CO2 at 0EC is given in the Table above.
a.

Plot PV as a function of P on a scale sufficiently expanded so that the experimental variations

in PV can be observed on the graph.

b.

From the plot, determine the value of RT at 0EC.

c.

The plot follows the equation, PV = RT + BP where B is an empirical constant. Determine

the value of B.

d.

On the same sheet plot PV versus P for an ideal gas.

e.

Calculate the value of PV at 0.90000 atm for 1 mol of CO2 at 0EC using the equation
determined in c. above. What would be the percentage error made if you used the ideal gas
law to calculate PV at 0.90000 atm for 1 mol of CO2 at 0EC ?

f.

Repeat the calculation in e. but at P = 90.000 atm. Comment on any difference in the
percentage error for the two calculations.

Assignment 3
Captain Kirk, of the Starship Enterprise, has been told by his superiors that only a chemist can be
trusted with the combination to the safe containing the dilithium crystals that power the ship. The
combination is the pH of solution A described below, followed by the pH of solution C. (Example:
If the pH of solution A is 3.47 and that of solution C is 8.15, then the combination to the safe is 3-478-15.) The chemist must determine the combination using only the information below (all solutions
are at 25C).

Solution A is 50.0 mL of a 0.100 M solution of the weak monoprotic acid, HX.

Solution B is a 0.0500 M solution of the salt NaX. It has a pH of 10.02.

Solution C is made by adding 15.0 mL of 0.250 M KOH to solution A.

What is the combination to the safe?

If, in preparing solution C, 15.0 mL of water was added instead of the 15.0 mL of KOH, what effect
would this have on the combination to the safe?

Show all calculations.

10

Assignment 4

The municipal water processing plants of communities with hard water often treat the water supply
with slaked lime, Ca(OH)2 , in order to remove Ca2+ from the water. The slaked lime reacts with
bicarbonate from the dissolved metal bicarbonates in the water according to the following reaction:
Ca(OH)2

+ 2 HCO3!

CaCO3 (s) +

CO32! + H2O .

The carbonate produced then reacts with Ca2+ originally in the water to precipitate as CaCO3 (s).
Thus calcium ions from slaked lime are added to the hard water in order to remove calcium ions from
the hard water!
If hard water has a calcium ion concentration of 1.8 x 10!3 M and you want to reduce that
concentration to 0.6 x 10!3 M, what must be the concentration of the slaked lime? If you didnt do
this calculation and you simply used a saturated solution of slaked lime, what do you think the
consequences might be? Support or refute your prediction by quantitatively assessing the likelihood
of your predicted consequences.

11

Assignment 5
a.

The sun supplies energy at a rate of about 1.0 kilowatt per square meter of surface area. The
plants in an agricultural field produce the equivalent of 20.0 kg of sucrose per hour per hectare
(1 ha = 10,000 m2 ). Assuming that sucrose is produced by the reaction
12 CO2 (g) + 11 H2O (l)

C12H22O11 (s) + 12 O2 (g)

H = 5640 kJ ,

calculate the percentage of sunlight used to produce the sucrose, i.e. determine the efficiency
of photosynthesis.

b.

The best solar panels currently available are about 15% efficient in converting sunlight to
electricity. A typical home will use about 40 kWh of electricity per day (kWh = kilowatt
hour). Assuming 8.0 hours of useful sunlight per day, calculate the minimum solar panel
surface area necessary to provide all of a typical homes electricity.

c.

Describe the methodology you followed in determining the minimum solar panel surface area
in question b. above. In your response provide a justification for each step you undertook in
solving the problem.

12

Lecture Note Supplement - Unit 2

Solution Equilibria
The following procedure allows one to deal quantitatively with any chemical system at equilibrium.
1.

Write balanced chemical equations to represent all of the reactions that occur in the system.

2.

List all species that exist in the system at equilibrium (omitting the solvent if it is present in
large excess).

3.

Write a number of independent, simultaneous equations, equal in number to the number of

species in the system, which relate the equilibrium constants for the reactions occurring and
the concentrations of the species in the solution. These equations will be of three types:
a.
b.
c.

equilibrium constant expressions,

mass balance equations and
a charge balance equation.

4.

Assess the values of equilibrium constants and concentrations that are known to determine
if it is likely that the concentration of any one species is negligible as compared to that of
another species. If this is so, it may be possible to simplify the mass balance and/or the charge
balance equations.

5.

After simplifying the equations where possible, solve the series of simultaneous equations for
the concentration or equilibrium constant that is being sought.

6.

Based upon the solution, check to ensure that any simplifying assumptions that were made
were valid.

7.

If the simplifications were justified, the problem is then successfully completed; if they were
not, then the full set of simultaneous equations must be solved.

A system at equilibrium can be quantitatively described by the following properties: C, the original
concentration of each reactant; V, the volume of each reactant; K, the equilibrium constant for each
reaction; and [species], the equilibrium concentration of each species present. If some of these
properties are known or measured experimentally, the others can be calculated by using the procedure
described above. For example, if C, V and K are known, the equilibrium concentration of all species
present can be calculated.
On the following pages are steps 1-3 of the general treatments of some common types of chemical
systems involving acids, bases and salts in aqueous solution.

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

Marking Scheme
Experiments: (5% each)

25

Quizzes (1.5% each)

7.5

Tutorial Assignments (1.5% each)

7.5

1 Hour Test - October 7, 2013

12.5

1 Hour Test - November 4, 2013

12.5

Final Exam - TBA, December 9 - 20, 2011

35

Total

100
All marks represent % of Total mark.

Policies Regarding Marks for Work Not Done or Submitted Late

Students are required to declare their absence from a class for any reason through their ROSI
accounts in order to receive academic accommodation for any course work such as missed tests, late
assignments, and final examinations. Absences include those due to illness, death in the family,
religious accommodation or other circumstances beyond their control In addition, students must
follow the instructions below.
1.

Experiments, Quizzes and 1 Hour Tests

All absences must be declared on ROSI. In addition, within one week of the date of the
missed work, students should submit to the course instructor a signed letter explaining the
reason for their absence. The letter should include the students name, phone number, e-mail
address, student number and lab section number as well as the date of and the description of
the missed work. For absence due to illness, an official U of T Medical Certificate is
required. That Certificate or other documentation appropriate to the reason for the absence
should be stapled to the letter. If the explanation is deemed reasonable (after the
documentation is verified), the final exam mark will be used as the mark for the missed
work. If the explanation is unreasonable or if no letter is submitted within one week of the
missed work, a mark of zero will be given for the missed work.
THERE WILL BE NO MAKE-UP EXPERIMENTS, QUIZZES OR 1 HOUR TESTS.

2.

Assignments
Unlike experiments and tests which can only be done on a particular day, assignments can
be done over a period of many days or weeks. Therefore medical or other excuses will not
be accepted as a reason for missing an assignment (excepting, of course, in the unfortunate
circumstance of a prolonged, serious illness).

3.

The penalty for late submission of an assignment or laboratory report is 5 marks off per
calendar day to a maximum of 7 days, after which a mark of zero will be given.

4.

Final Examination: Refer to the UTM Academic Calendar for these regulations.

31

General Laboratory Instructions

We should first of all consider why laboratory experience is an essential part of any university
science program. Why is it very important to learn to make careful observations and experimental
measurements in the laboratory?
All of our accumulated understanding of the physical world ultimately depends on the large
number of careful experimental observations that have been made by many generations of scientists
since the beginning of recorded history, and to which research scientists are adding every day. In
chemistry it is convenient to divide experimental observations into two main categories: those that
we refer to as qualitative observations and those that we refer to as quantitative observations.
Qualitative experiments involve observations with our normal physical senses, such as sight and
smell. For example, the observation of a color change in a chemical reaction is a qualitative
observation. Quantitative observations involve the measurement of some physical quantity such as
mass, volume, pressure, concentration or temperature. Whether we are making a qualitative
observation or a quantitative measurement in the laboratory, it must be done as carefully as possible
and reported with complete honesty.
It is of the greatest importance that all of the observations that you make during this
laboratory course be recorded immediately in this manual which also serves as your
laboratory notebook. If you are doing a qualitative experiment, immediately describe as carefully
and as accurately as you can what you actually observe, no matter what you might have anticipated
on the basis of previous knowledge or theoretical considerations. If you are making a quantitative
measurement, immediately record any quantity that you measure with its correct units. If you think
that the result is strange or unusual, say so, but do not tamper with the results. There is no place for
fiction in the chemistry laboratory. There is no such thing as an incorrect experimental result. Many
new discoveries have resulted from experiments that went wrong or did not fit the theory.

32
Honest mistakes can of course occur and inaccuracies may result from lack of care or imprecision
in making measurements. That is why we repeat experiments when we can, so that we have a basis
for deciding what results might legitimately be discarded. When you get an unusual or imprecise
result you should always try to understand why. What was there about the experimental procedure
that might have led to error? Consult your TA if you are puzzled about a result or think that you may
have carried out some procedure inaccurately.
The final objective of many experiments is simply to support our understanding of well
understood concepts and theories. In others we may be interested in improving an experimental
procedure to get a more accurate result or to improve the yield of a compound that we are making.
If you can think of ways in which an experiment could be improved, say so. In general, however,
especially in university, an important objective is to use new experimental observations as the basis
for improving existing theories or formulating new concepts that will ultimately lead to better
theories that embrace more experimental observations than the old theories. The results of careful
experiments have a timeless quality; they are, indeed, the permanent body of knowledge that
constitutes science. Scientists may repeat your experiment in the future; if it is accurate they will
still get the same result. The only difference might be that they can improve the accuracy of a
physical measurement because they have improved measuring instruments. In contrast, theories are
simply the best models that we can formulate to tie together as many as possible of the facts that are
known today. As new results accumulate old theories are discarded and replaced by new ones.
The object of a laboratory course, therefore, is not simply to mindlessly get correct answers
but to learn to understand how to handle common laboratory apparatus and what needs to be done
to get reliable results. In terms of rewards, both short-term and long-term, a careful approach and
an aware, enquiring mind count for far more than a slavish attempt to reproduce what the instructions
or textbooks say is right.

33
1.

Materials
YOU WILL NOT BE ALLOWED TO WORK IN THE LABORATORY WITHOUT
ALL OF THESE MATERIALS !!
a.

This Course Manual/Notebook (the entire manual, not just selected pages) must be
brought to all laboratory classes.

b.

A laboratory coat (100 % cotton recommended although other materials are

acceptable) to protect you and your clothes is mandatory.

c.

Indirectly vented chemical splash safety goggles ( on sale in the Bookstore) must be
worn at all times in the laboratory. Gloves are required for some procedures.

2.

Safety Precautions
Experimental chemistry is inherently dangerous; many experiments can be hazardous unless
the experimentalist is aware of the nature of the materials used and is careful in handling
them. The best precaution against accident is to understand what you are doing and to keep
a neat and well-organized laboratory bench.
THE FOLLOWING PRECAUTIONS MUST BE OBSERVED.
a.

Eye protection must be worn at all times. Indirectly vented chemical splash safety
goggles are on sale in the Bookstore. (N.B. Concentrated alkalies, such as 30%
sodium hydroxide, can dissolve the cornea instantaneously.)

b.

If a chemical accidentally gets in your eyes, in your mouth, or on your skin, rinse the
affected area immediately with plenty of cold water. Do not delay in doing this,
whether it involves you or a neighbor. Immediate action can prevent a serious injury.
Then report the accident to your TA or the technician, who will decide if further
treatment is needed.

c.

Never taste a chemical. Consider all chemicals as potentially toxic. Always wash

34
your hands before leaving the laboratory.
d.

Clean up chemical spills immediately. For acid or base spills, rinse off with water
and inform the TA or technician.

e.

Read the labels on all reagent bottles carefully. Be sure that you know what
chemical you require and in what quantity. If it is a solution, carefully check the
label to make sure it is in the correct concentration. Serious hazards can result from
mixing (mistakenly) certain solutions.

f.

Never pipet by mouth. Your TA will show you how to measure out fixed volumes
of solutions using a pump or a rubber bulb on the pipet.

g.

Perform the experiment in a fume hood if corrosive or toxic vapors are in any way
involved in the experiment.

h.

Dispose of waste materials properly.

(1)

Broken glass should be put only in the containers marked Glass.

(2)

Waste chemical solids should be disposed of in the special containers

provided. Do not mix waste chemicals and waste paper.

(3)

Check with your TA before disposing of any waste liquids down the sink.
For certain liquids, special waste containers will be provided.

i.

Eating and drinking are strictly forbidden in the laboratory.

j.

Dress appropriately. Do not wear sandals or shorts. Tie back long hair. A lab coat
is mandatory.

3.

Laboratory Practice
a.

Reagents. These are usually obtained from stock bottles. If you contaminate the
stock bottle or remove unnecessarily large amounts of a reagent, then you have

35
committed an anti-social act.
(1)

Never remove reagent bottles from the supply area.

(2)

When using stock reagents, keep the bottle stoppers clean and always replace
them after use.

(3)

Know how much reagent you require and take only the amount needed.

(1)

Use a clean, dry spatula in handling solids.

(2)

Never insert a pipet into a reagent bottle. Instead, transfer the necessary
solution to a clean, dry beaker and pipet from the beaker.

(3)
b.

Never return unused chemicals to the stock reagent bottles

Balances. Two kinds of balances are available. For the most accurate weighings,
use an analytical balance. For weighings that require less accuracy, use a triple-beam
balance. Make sure that you know which balance is required for a particular
weighing. Under no conditions should reagents be allowed to come into contact
with the balance pans. When using the analytical balance weigh by difference from
a clean, dry weighing bottle. If you have an accidental spill, report it immediately to
your TA or technician. When using the triple-beam balance, weigh by difference into
a clean beaker or onto a clean piece of weighing paper.

c.

Distilled Water. The supply of distilled water is limited. Use it only for the final
rinsing of glassware. It should also be used for making up all aqueous solutions. The
use of ordinary tap water can lead to spurious results.

d.

Experimental Hints
(1)

Cleanliness is essential. Clean all glassware and rinse with distilled water.

(2)

For reactions which need to be carried out at elevated temperatures, a hot

36
plate or a hot water bath on a hot plate should be used.
(3)

In separating a precipitate from a solution by centrifugation, be sure that the

centrifuge is properly balanced.

(4)

Whenever reagents are combined, be sure that the resulting solution is

thoroughly mixed. Diffusion in solution can be a very slow process.

4.

The Laboratory Notebook

Laboratory work may not be done without this Manual (used also as a Notebook).
This notebook is your most important piece of equipment in the laboratory, so important that
you should never be in the laboratory without it. It is used to keep a record of all the details
and observations of the experiments performed. The following guidelines should be
observed.
a.

Record all entries in permanent, water-proof ink. If for some reason you want an
entry to be disregarded, it should be crossed out (not erased) and the reason for
disregarding it should be noted

b.

Before coming to the laboratory, read the experiment carefully. Answer all the prelab questions for the experiment. Pre-Lab Questions must be handed in to your
TA as soon as you enter the lab. This will be followed by a 5 minute lab quiz.
The quiz question will be one of the pre-lab questions. This must be written and
handed in before you begin any experimental work.

c.

Any procedures used, if they differ from the instructions given and any observations
made should be recorded in the notebook on the back of the data sheet as the
experiment is being performed. This can be done in note form. If you are using a
balance, take your notebook with you to the balance to record your data. Trying to

37
remember afterwards or jotting down observations on scraps of paper is unreliable
and represents poor laboratory technique.
d.

5.

Before leaving the laboratory, have your pages of data initialed by your demonstrator.

The Report
Reports should contain the following items:
a.

a Cover Page containing your name and student number, the full name of your lab
partner if you worked in pairs, your lab section number, your TAs name; the number
and title of the experiment, the date on which it was performed and the date on which
the report was submitted;

b.

a few lines, with chemical equations where applicable, describing the Purpose of the
experiment;

c.

the Experimental Method - the actual record of how the experiment was done,
taken from your notebook record. Deviations from the procedure given in the
manual should be described in detail. The instructions in this manual should not
be mindlessly rewritten in your report, but should be referenced. Therefore this
section may be very brief unless there were significant deviations from the procedure
in the Course Manual.;

d.

the experimental Results including observations, tables of data, calculations and

graphs where appropriate and answers to any questions in the text of the experiment;

e.

a brief discussion of the results which may include comparison with theory,
quantitative assessment of precision and accuracy, explanation of errors, or
suggestions for improvement of the experiment;

f.

a Summary of the results and conclusions, given in a few lines (or in a table if

38
appropriate);
g.

References - the source of any information written in your report that was obtained
from books, journals, websites or other sources:
(1)

(2)

(3)

books
Author
Title
; Publisher
:
Place
th
Zumdahl, S. Chemical Principles, 6 edition; Brooks/Cole.: Belmont,CA;
Year Page
2009; p 47
journals
Author
Journal
Year, Vol., Page
Aggarwal, V.A. J. Am. Chem. Soc. 1996, 118, 7004
websites
last
Author
Title
URL
update
Hsu, D. Chemicool Periodic Table ; http://www.chemicool.com; Aug. 5,
2013

h.

The Data Sheets from this Manual should be attached at the end of the report.

i.

For Experiments 1, 3 and 4, the report should also address the Writing Initiative
assignment for that experiment (found immediately before the pre-lab questions for
that experiment). This part of the report should be a maximum of one page, with 1.5
line spacing, 12 point Times New Roman font, and 3/4 inch margins. Your name,
student number, PRA section number and TAs name should be printed in a single
line at the top of the page. This should be handed in at the same time as the rest of the
report but should not be stapled to it.

All reports must be prepared with the use of word processing and spreadsheet programs
If you are not familiar with the use of spreadsheets, visit the following website for
instruction: http://library.utm.utoronto.ca/excel .
Reports are due as listed in the Schedule on page 3.

39
7.

Marking Scheme for Laboratory Reports

The nature of each experiment is different and therefore each will have a different marking
scheme. For example, in some qualitative observations are most important, in others,
quantitative calculations and graphs are prominent. However 10% of each report mark will
be for report presentation. This refers to formatting, appearance, grammar, spelling, clarity,
and following the report guidelines given above. The writing assignment in the reports for
Experiments 1, 3 and 4 will each count for 15% of the total report mark. Another 10% of
each report mark will be for experimental technique. This refers to your actual performance
in the laboratory. The table below lists some common ways that technique marks are lost.
As you can see they are easy to avoid.
Infraction

Mark Deduction

Infraction

Mark Deduction

not bringing goggles*

-2

not recording data in

permanent ink

-3

not bringing lab coat

-2

leaving a mess
around the balances

-2 (for everyone in
the section)

not reading
equipment to its
tolerance level

-3

leaving a dirty
workstation at the
end of the lab period

-2

accidentally breaking
0
glassware**
*Students are not allowed in the lab without safety goggles. There is a limited supply of goggles that
may be borrowed from the lab technician, at a cost of 2 marks. If this supply runs out and you dont
have goggles, you will not be allowed in the lab and will get zero for that experiment mark..
**NB While there are no deductions for accidently breaking glassware, this is contingent on you
reporting any breakages to your TA. Not reporting broken glassware is a major safety violation and
will carry a significant mark deduction.

8.

Integrity and Ethics in the Laboratory

A scientists most valuable possession is integrity. Be a scientist! Be conscientious
in your efforts to observe, collect, record, and interpret the experimental data as best as you

40
can. In CHM110H and at the University of Toronto Mississauga, only honest scientific work
is acceptable.
Occasionally you make a measurement that you think is incorrect. At such a time you
may be tempted to change the measurement or to copy the measurement of another student.
I urge you to strongly resist this temptation. A person who alters their data is of no use in
the scientific community. As well, the academic penalties for such behaviour are severe, the
minimum penalty being a mark of zero for that experiment and the notation of an academic
offence on your official academic record.
From the Code of Behaviour on Academic Matters:
It shall be an offence for a student knowingly:
(d) to represent as ones own any idea or expression of an idea or work of another in
any academic examination or term test or in connection with any other form of
academic work, i.e. to commit plagiarism.
The quotation above is taken from an excellent article written by Senior Lecturer Emeritus,
Margaret Procter, entitled How Not To Plagiarize. It is well worth reading and can be
found at the following address:
http://www.writing.utoronto.ca/advice/using-sources/how-not-to-plagiarize

41
EXPERIMENT 1
Separation of Metal Ions by Paper Chromatography
Introduction
The first use of chromatography was described by the Russian botanist, Mikhail Tsvet, in
1906. He used a solvent to carry coloured material extracted from vegetables along a length of paper
and demonstrated the separation of - and -carotene. Tsvet named the process chromatography, from
the Greek for colour writing (chromos and graph). Today the term applies to a number of methods
for separating the components of a mixture on a support material.
In paper chromatography, a sample spot of the mixture to be analyzed is applied on to an
adsorbent paper (the stationary phase). The end of the paper is then dipped into a solvent (the mobile
phase) which then rises up the paper by capillary action. As the solvent passes over the sample spot,
the components of the mixture are attracted to the solvent and are carried with it up the paper. But
the rate at which each component of the mixture is carried up depends upon how strongly the
component is attracted to the paper as compared to how strongly it interacts with the solvent. As a
result, each component of the mixture rises up to a different position on the paper thus separating the
components of the mixture. The ratio of the distance that a compound rises up the paper to the
distance that the solvent moves up the paper is called the retention factor, Rf. The Rf values for
compounds are dependent on the solvent and the temperature.. If the components of the mixture are
coloured, their positions on the paper can be seen by eye. If they are colourless, they can be detected
by viewing the paper under UV light or by exposing the paper to another compound that reacts with
the components to form coloured compounds.
In this experiment the Rf values for five different transition metal cations will be determined.
In addition, an unknown mixture of some of these cations will be analyzed.

42
Pre-lab Questions
Answer the pre-lab questions found on pages 49-50 . Those pages must be removed from this
manual and submitted to your TA when you enter the laboratory.
Procedure
In this procedure you will apply eight sample spots to a piece of chromatography paper: one spot of
each of the five metal ion containing solutions, one spot of a solution that contains all five of the
metal ions, and two spots of your unknown solution (which will contain from 2 to 4 metal ions).
After the spots dry, the paper will be dipped into the solvent in the developing chamber and the
chromatogram will be allowed to develop. When the solvent front has reached up to within about 1.51.0 cm of the top of the paper, the paper will be removed from the developing chamber and the
solvent front will be marked with a pencil. When the paper is dry, any visible bands will be circled.
The chromatogram will then be enhanced by being placed in the ammonia chamber for 5-10 minutes
and any additional bands that appear will be circled. Finally, the bands will be further enhanced by
reaction with the reagents listed in the Table. Note that gloves must be worn for all work with the
developing solvent and the ammonia chamber and this work MUST be done in the fume hood.
Gloves should also be worn when handling the chromatography paper.
1.

Preparation of the Developing Chamber

Using a graduated cylinder, measure out approximately 10mL of the developing solvent (a 9:1
mixture of acetone:6M HCl). Pour the solvent down a glass stirring rod into the middle of
a dry 600mL beaker. It is important that you do not wet the sides of the beaker. It is also
critically important that the height of the liquid in the beaker is less than 1cm. Cover
the beaker tightly with plastic wrap in order to allow the atmosphere in the beaker to become
saturated with the vapour of the solvent. (Saturation takes about 10 minutes.)

2.

Preparation of the Ammonia Chamber

43
The ammonia chamber consists of an 800/1000mL beaker in the center of which is a 30/50mL
beaker which contains about 5mL of concentrated aqueous ammonia solution. The larger
beaker is covered tightly with plastic wrap. This chamber will have been preassembled for
you and will be in your fume hood. Check to see that there is about 5mL of ammonia solution
in the small beaker. If there is not, ask your TA or the technician for asistance in topping up
the ammonia level. This chamber must be kept in the fume hood and must be tightly
covered with plastic wrap at all times excepting when placing or removing the
chromatography paper.

Figure 1. Preparation of the Chromatography Paper

3.

Preparation of the Chromatography Paper

Wearing gloves, obtain one 10cm x 20cm chromatography paper and place it on a clean piece
of ordinary white paper, not directly on the lab bench. Always wear gloves when handling
the chromatography paper. With a pencil, measure and mark the chromatography paper as
shown in Figure 1 above. Where the tick marks cross the 1.5cm line is where you will apply
the sample spots

44
4.

Applying the Sample Spots

The liquid sample spots will be applied to the chromatography paper using a capillary
tube. The best chromatograms result from small, compact sample spots. Aim for a spot size
between 2 and 4 mm in diameter. You may wish to practice by spotting distilled water along
the top 20cm edge of the paper, confining the water spots to within 1cm of the top of the paper.
Once you are confident of your spotting skill, proceed to apply the sample spots.
You will find six labelled solutions in test tubes on your bench, five of which contain
one metal ion and one of which contains a mixture of all five metal ions. Obtain a seventh
solution, your unknown solution, from your TA. Using a different capillary tube for each
solution, apply one drop of each of the solutions at the marks on the chromatography paper.
Allow the paper to dry. Then repeat the spotting and drying procedure two more times in order
to increase the metal ion content in each sample spot. N.B. Be careful not to mix up the
capillary tubes! BE PATIENT. It is essential that each spot is dry before applying the
next drop of solution on that spot. If it is not dry, the spots may spread and contaminate
each other.

5.

Developing the Chromatogram

Roll the dry chromatography paper into a cylinder with a small gap, ~0.5cm, between
the edges as shown in Figure 2 below. With a piece of tape, ~1.5cm long, connect the two
edges of the paper. Be sure that the two ends of the paper are not touching and that the
cylinder is secure and will not easily come apart. Double check the developing chamber to
ensure that the liquid level is less than 1 cm high. It is essential that when the paper is
put into the chamber, the sample spots are above the liquid level.

45

Figure 2.
Remove the plastic wrap from the developing chamber and carefully put the paper
cylinder into the chamber being careful that the paper does not tough the walls of the beaker.
Carefully replace the plastic wrap without disturbing the chamber. Observe what happens as
the solvent moves up the paper and record your observations.
When the solvent has moved up to about 1.5 cm from the top of the paper (~ the 500mL
mark on the beaker), remove the paper from the chamber, unroll it on a clean piece of white
paper and mark the line of the solvent front with a pencil. It is important that this be done
very quickly as the solvent evaporates quite quickly and you must know where the
solvent front was in order to later calculate the Rf values. Then recover the developing
chamber with plastic wrap. Allow the solvent to evaporate from the paper and then circle all
of the visible bands with a pencil. Record your observations.
6.

Enhancement of the Chromatogram

Roll the paper back into a cylinder, secure the cylinder, and place it in the ammonia chamber
and replace the plastic wrap. When a band for each known cation is visible, after about 5
minutes, record your observations. Remove the paper from the ammonia chamber but leave
it in the fume hood to let the ammonia evaporate. Circle all visible bands. It is important
that this be done quickly as some visible bands disappear. Be sure to tightly cover the

46
ammonia chamber with a new piece of plastic wrap. Table 1. identifies the colours of the
cations in the presence of ammonia.
Table 1. Ammonia Test and Confirmatory Test Colours

NH3 Test

Mn+2

Fe+3

Co+2

Ni+2

Cu+2

Tan

Red-Brown

Pink (Brown)

Light Blue

Blue

0.2M KSCN

Saturated
KSCN in
acetone
Blue-Green

0.1M
NaHDMG*

K4[Fe(CN)6]

Brick-Red

Red

Confirmatory
Test Reagent
Band Colour
*DMG = dimethylglyoxime
7.

Blood-Red

Confirmatory Identification of Bands

To confirm the presence of the cations and to enhance the location of some of the
cations, the bands can be reacted with the reagents as listed in Table 1. Use a capillary
tube to spot the center of each band with the corresponding reagent as identified in the
Table. Remember that the unknown solution may contain from 2 to 4 cations. Circle all
visible bands and record your observations.

8.

Clean-up
Return your unknown solution to your TA. Dispose of the used developing solution
in the bottles marked Organic Waste in the common fumehood. Rinse the 600mL beaker
with distilled water and dry it with a paper towel. Dispose of the used capillary tubes in the
bucket marked Broken Glass. Ensure that your lab bench and fume hood are clean and
dry. Make sure that the the ammonia chamber is securely covered with plastic wrap.

Analysis of the Chromatogram

1.

Write an equation for the reaction of each of the metal ions with ammonia that leads to the
coloured band observed.

2.

Write an equation for the reaction of each of the metal ions with its confirmatory reagent.

47
3.

Mark the center of the band for each cation. Measure the distance travelled by each cation.
Calculate the Rf value for each cation

4.

Calculate the Rf value for each of the components of your unknown and by comparison
with the chromatogram of the known ions, identify the components of your unknown.

Writing Assignment
Gas chromatography (GC) is done in the gas phase. A
gas chromatograph (GC) has three parts: a sample
introduction system (injector), an oven containing a
chromatography column to achieve separation, and a
detector. In drug testing, a microliter of liquid urine
extract is injected into the injector, a chamber at a high
temperature. The sample is vaporized and swept along a
hair-thin glass tube (capillary column, many meters long,
flexible enough to be rolled up in a coil) by a carrier gas
(mobile phase), such as helium. Different compounds
travel at different speeds because of the differences in
boiling point, polarity, and relative solubility in the carrier
gas versus the coating of the inner wall of the column
(stationary phase). The compounds emerge from the
column outlet at different times after injection (the
chromatographic retention time)separated from each
other. Under identical operating conditions, the retention
time is characteristic of each chemical compound. If two
compounds have the same retention time, they may be
identical (eg, testosterone). If two compounds have
different retention times, they certainly are different (eg,
testosterone and methyltestosterone). Matching retention
times between an unknown and a reference standard is
one element of identification. A graph of the amount of
substance as a function of the retention time is a
chromatogram.

Fig.. GC-MS data for designer steroid madol.

(A) GC chromatogram; the isomer differs only by the position of the double bond.
(B) MS full scan.
(C) MS selected ion monitoring (SIM) scan

48
Mass spectrometry (MS) is an analytical chemistry technique used for structure elucidation of
unknowns or identification of known compounds. A mass spectrometer has three parts: an ion
source where the compound is ionized to form a molecular ion and fragmented into smaller ions; a
mass filter that separates ions by mass-to-charge ratio (m/z); and a detector. The graph of ion
abundance as a function of m/z is a mass spectrum. In Figure 2B, the molecular ion is 360 and
significant ions are 345 and 143 (largest = base peak = 100%). The fragmentation pattern is
determined by weak bonds and other physicochemical characteristics; therefore, fragmentation is
reproducible and characteristic of the molecular structure, and the mass spectrum is like a
fingerprint of the compound. Matching mass spectra between an unknown and a reference standard
is another element of identification. Significant ions are so characteristic that matching only three
ions (eg, 143, 345, 360) and their percent abundance relative to the most intense of the three (eg,
143) has long been widely accepted as proof of chemical identification.
http://www.antidopingresearch.org/BeyondSportsDopingHeadlines.pdf
The combination of gas chromatography and mass spectrometry, GC-MS, is a powerful analytical tool
commonly used in drug analysis. Components of a mixture, commonly a urine sample, are separated
using gas chromatography and identified from their fragmentation patterns in the mass spectrometer.
Describe why the combination of these two techniques is so much more effective an analytical tool
than is either on its own. Imagine yourself to be a lawyer for an athlete who tested positive for an
anabolic steroid. In preparing the case for the defense what questions would you ask about the GC-MS
testing that was done?

49
Name:___________________________

Student No.:____________________

Lab Section No.:___________________

Pre-lab Questions
1.

Explain why it is important to mark the chromatography paper with a pencil and not with a
pen.
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

2.

What is the stationary phase and what is the mobile phase in this experiment?
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

3.

What would happen in this experiment if the solvent level in the developing chamber was more
than 1.5cm high, i.e. if the sample spots were below the solvent level?
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

4.

If two cations have the same Rf value, how could you detect their presence in a mixture using
paper chromatography?
_________________________________________________________________________
_________________________________________________________________________

50
_________________________________________________________________________
_________________________________________________________________________
5.

In the chromatogram of a Zn+2 containing solution, the Zn+2 travelled 24mm and the solvent
front travelled 94mm. In another chromatogram of a solution of a mixture of cations, the
solvent front travelled 87mm. If Zn+2 was in that mixture, where would its band appear on the
paper?
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

51
Name:____________________________

Student No.:_____________________

Lab Section No.:____________________

Date:__________________________
Data Sheet

Unknown No.:_______________
Room Temperature:___________
OBSERVATIONS
Sample

Mn+2

Fe+3

Co+2

Ni+2

Cu+2

5 cation
mixture
unknown

unknown

Observed
Colour after
Developing
Chamber

Observed
Colour after
Ammonia
Chamber

Observed
Colour with
Confirmatory
Reagent

Distance
Travelled
by ion (mm)

Distance
Travelled
by the
Solvent
(mm)

52

53
Experiment 2
BEHAVIOR OF GASES

Part A.

DETERMINATION OF THE ATOMIC MASS OF A METALLIC ELEMENT

Introduction
The atomic mass of a metal can be determined by several methods. Two of these are based
upon the reaction of the metal with aqueous acid:
M(s) + n H3O+

M+n(aq) + n/2 H2 (g) + n H2O

The atomic mass can be determined by either (1) determining the number of moles of H2 gas produced
by a known weight of metal, or (2) determining the number of moles of H3O+ that are consumed by
a known weight of metal. In this experiment the former method will be used.

Pre-lab Questions
Answer the pre-lab questions on pages 61 and 62. 1-3 refer to Part A of the experiment; 4 and 5, to
Part B..

54
Procedure
1.

The apparatus for this part of the experiment consists of an 800/1000 mL beaker and a 50 mL
gas burette set up as shown below

55
1.

Mix 350 mL of distilled water with 150 mL of 1 M HCl solution in an 800/1000 mL beaker.
Fill the gas burette with this solution and, wearing a glove, close the open end with your finger
and invert the burette in the solution remaining in the beaker. Clamp the burette vertically,
with the end immersed just below the surface. Take care that air bubbles are not trapped in the
gas burette. Wash your hands.

3.

Obtain an unknown metal from your TA. Clean an approx. 2 cm strip of a 3 mm wide metal
ribbon by rubbing with a small piece of sand paper until the metal is bright and no black spots
are left on the surface. Wipe the clean metal with tissue or filter paper and then weigh it,
accurately to 0.1 mg, without handling.

4.

Fold the metal two or three times into a fairly compact mass and press it into a 3-in. test tube.
It should fit snugly against the walls. Fill this tube with distilled water; then, wearing a glove,
insert it, open end up, into the end of the gas burette and lower the gas burette to hold the tube
captive. The acid will diffuse into the test tube and react with the metal. The H2 evolved will
then collect in the gas burette and displace the dilute acid. Wash your hands.

5.

When all the metal has reacted, measure the volume (V, mL) of the gas and the temperature
of the solution in the beaker. It can be assumed that the temperature of the gas in the burette
(T, EK) is the same as that of the solution. Also measure the difference in height (h, mm) of
the solution levels in the burette and in the beaker, and record the atmospheric pressure
(Patm, torr).

Calculations
1.

The total pressure of the gas trapped in the burette will differ from the atmospheric pressure
by the hydrostatic pressure exerted by the difference in liquid levels in the burette and in the
beaker. This hydrostatic pressure was measured in millimetres of solution (h); it can be
readily expressed in torr, since
soln hsoln = HghHg

and

1 torr = 1 mm Hg

The density of the solution soln, may be considered equal to that of H2O at 1.00 g/mL; the

56
density of Hg is 13.6 g/mL. Calculate the hydrostatic pressure in torr.
2.

The total pressure of the gas trapped in the burette can now be calculated. However, this gas
is a "mixture" of H2 and H2O vapour, and
PH2 + PH2O

pressure inside of burette

The vapour pressure of H2O in the mixture can be estimated from the temperature of the
solution using the data in the Table below, assuming that the vapour pressure of water over the
dilute hydrochloric acid solution does not differ appreciably from that over pure water. Plot
a graph of the data in the Table and read off the P corresponding to the temperature of your
experiment.

Note that if the level of liquid in the beaker and the burette are equal,

PH2 + PH2O

Patm.

If the level of liquid in the burette is higher than in the beaker, the pressure in the burette is less
than atmospheric pressure, and
PH2 + PH2O

Patm - Phydrostatic.

Calculate the total pressure of the gas trapped in the burette.

EQUILIBRIUM VAPOUR PRESSURE OF WATER

T (oC)

16

18

20

22

24

26

28

30

P (torr)

13.6

15.5

17.5

19.8

22.4

25.2

28.3

31.8

3.

Calculate the pressure of the trapped H2 gas.

4.

From the values of PH2, V, and T, calculate the number of moles of H2 using the ideal gas
relation. Check that your answer here is reasonable as compared to the answer to Pre-lab
Question 3.

5.

From the stoichiometry of the reaction and the number of moles of H2 evolved, calculate the
number of moles of metal in the sample. Assume that n in the balanced equation for the
reaction is either 2 or 3. From the weight of the sample, then determine the two possible

57
atomic masses of the metal. Consult the Periodic Table to see which more nearly corresponds
to a known metallic element.

Part B.

GRAHAMS LAW OF DIFFUSION

Introduction
Effusion describes the passage of the molecules of a gas through a small hole into an evacuated
chamber. This term is often confused with a similar term, diffusion. Diffusion is the spreading out
of gas molecules through space when a container of gas is opened, allowing the gas to mix freely with
any other gases present.
According to the kinetic-molecular theory of gases, the average velocity of the particles in a
sample of gas is inversely related to the square root of the molar mass of the gas. In the nineteenth
century Thomas Graham, a Scottish chemist, determined experimentally that the relative rate of
diffusion of two different gases at the same temperature was given by the relationship
r1 /r2

(M2 / M1)

in which r represents the rate of diffusion of a gas and M its molar mass. This equation, Grahams
Law, is consistent with the kinetic-molecular theory.
While it is not possible experimentally to determine easily and directly the average velocity of
the gas molecules, the rate of diffusion can be determined by measuring how long it takes a gas to pass
through a tube of known length.
In this experiment you will determine the relative rates of diffusion of the gases hydrogen
chloride and ammonia by measuring the distances travelled by the two gases in the same time period.
For a given period of time, the lighter weight gas should diffuse farther than the heavier gas (since
distance travelled in a given time period is directly proportional to rate). The two gases will
simultaneously be introduced to opposite ends of a hollow glass tube. The gases will diffuse through
the tube toward each other and when they meet they will react with each other forming the salt,

58
ammonium chloride. The resulting white ring of ammonium chloride that forms will indicate the
position in the tube at which the gases meet.
HCl(g) + NH3 (g)

NH4Cl(s)

Procedure (work in pairs)

CAUTION: This procedure involves the use of concentrated acid and base. Eye protection and
gloves must be worn at all times. The fumes from these chemicals are extremely irritating and
are dangerous to the respiratory tract. These chemicals must be confined to the fume hoods at
all times.
1.

Obtain three ~1 cm diameter glass tubes of equal length and two stoppers that will fit snugly
in the ends of the tubes. Measure the length of the tubes.

2.

Set up a tube in the fume hood using two adjustable clamps to hold the tube in a steady
horizontal position.

3.

In the fume hood will be a small beaker of concentrated HCl and a small beaker of
concentrated NH3, each covered with a watch glass. (Leave the beakers covered when not in
use.)

4.

USING FORCEPS to hold the cotton balls, briefly dip one cotton ball into each of the
solutions. (The cotton balls will dissolve if left too long in the solutions!) Immediately
transfer the cotton balls from the solutions to the opposite ends of the glass tube, inserting the
two cotton balls simultaneously. Stopper the ends of the tube and do not disturb or move the
tube.

5.

Patiently watch while the gases diffuse toward each other. When they meet, a white ring of
ammonium chloride will appear. Mark the position on the tube where the ring first appears
and, with a ruler, measure the distance of the white ring from the cotton ball at each end of the

59
tube. (As the gases continue to diffuse, the position of the ring will blur so the tube must be
marked as soon as the white ring appears.)
6.

Remove the stoppers from the tube and, using forceps, remove the cotton balls and place
them in the large beaker of water that is in the fume hood. Carefully place the glass tube in the
large plastic container in the fume hood.

7.

Repeat the experiment with each of the other two tubes.

Calculations
1.

From your three sets of data, calculate the average distance diffused by HCl and by NH3.

2.

Using these average distances and assuming that the distance travelled is directly proportional
to the rate of diffusion, calculate the ratio of diffusion rates for the two gases, rNH3 / rHCl .

3.

Calculate the ratio of diffusion rates of these two gases that would be predicted by Grahams
Law.

4.

Calculate the % deviation of your experimental results from the Grahams Law prediction and
comment on this deviation.

60

61
Name:

Student No.:

Lab Section No.:

Pre-lab Questions

1.

Would a change in the concentration of HCl used in Part A of this experiment affect the result?
Explain.

2.

If H2SO4 were used in place of HCl in Part A of this experiment, would this have changed the
volume of gas evolved? Explain.

3.

What is the maximum number of moles of H2 that could be collected in Part A of this
experiment if T = 20EC and Patm = 760 torr?

4.

What error would be introduced in Part B of this experiment if the NH3 was introduced to the
glass tube substantially before the HCl?

62

5.

How would you expect the result of Part B to differ if the experiment was done at a higher
temperature?

63
Data Sheet
Name:
Student No.:
Lab Section No.:
Date:
Name of Lab Partner:______________________________________________________
Part A
weight of metal strip
volume of gas in burette
temperature of solution
h of solution levels
atmospheric pressure
Observations:

Part B

Distance of Ring of NH4Cl from Cotton in

Trial No.
1
2
3
Temperature
Observations:

Length of Tube

NH3 End of Tube

HCl End of Tube

64

65
EXPERIMENT 3
Analysis of Antacids by Acid-Base Titration

Introduction
Hydrochloric acid is one of the substances found in gastric juices secreted by the lining of
the stomach. HCl is needed by the enzyme pepsin to catalyze the digestion of proteins in the food we
eat. Heartburn is a symptom that results when the stomach produces too much acid (hyperacidity).
Antacids are bases used to neutralize the acid that causes heartburn. Despite the many
commercial brands, almost all antacids act on excess stomach acid by neutralizing it with weak bases.
The most common of these bases are hydroxides, carbonates, or bicarbonates. The following table
contains a list of the active ingredients found in several common commercial antacids, and the
reactions by which these antacids neutralize the HCl in stomach acid.

Compound

Formula

Chemical Reaction

Aluminum hydroxide

Al(OH)3

Al(OH)3(s) + 3 HCl(aq) -----> AlCl3(aq) + 3 H2O(l)

Calcium carbonate

CaCO3

CaCO3(s) + 2 HCl(aq) -----> CaCl2(aq) + H2O(l) + CO2 (g)

Magnesium carbonate

MgCO3

MgCO3(s) + 2 HCl(aq) -----> MgCl2(aq) + H2O(l) + CO2 (g)

Magnesium hydroxide

Mg(OH)2 Mg(OH)2(s) + 2 HCl(aq) -----> MgCl2(aq) + 2 H2O(l)

Sodium bicarbonate

NaHCO3 NaHCO3(aq) + HCl(aq) -----> NaCl(aq) + H2O(l) + CO2 (g)

In this experiment, several brands of antacids will be analyzed to determine the number of
moles of acid neutralized per tablet and the cost analysis of each tablet. The analytical procedure used

66
is known as back titration. In this procedure, a known amount of HCl, which is in excess of the base
in the tablet sample, will be reacted with a weighed sample of a ground antacid tablet. The HCl
remaining after the antacid neutralization reaction occurs will be determined by titration with a
standardized NaOH solution to a bromophenol blue endpoint. The number of moles of HCl neutralized
by the antacid is the difference between the moles of HCl initially present in the excess added and the
moles of HCl titrated by the NaOH.. *
*www.chem.latech.edu/~deddy/chem104//104Antacid.htm
Pre-lab Questions
Answer the pre-lab questions on page 71.
Procedure
1.

Obtain two different brands of commercial antacid tablets from your TA. For each record the
brand name, the number of tablets in the bottle, the cost per bottle, and the mass of the tablet
and of the components of the tablet as described on the label. Grind one of the antacid tablets
with a mortar and pestle to a fine powder. Weigh out approximately 0.2g of the powder into
each of two 125mL or 250mL Erlenmeyer flasks (the mass should be accurately measured to
0.0001g.

2.

Pipette 25.0mL of standardized ~0.1M HCl into each of the flasks and swirl to dissolve the
powder. Be sure to record the actual concentration of the HCl solution.

3.

Put the flasks on a hotplate, heat to a very gentle boil with occasional swirling and maintain
the heat for about 1 min to remove any dissolved CO2.. Remove the flasks from the hotplate
(caution: the flasks are hot) and add about 6 drops of the indicator, bromophenol blue. This
indicator is yellow at pHs below 3.0 and blue at pHs above 4.6. Swirl the flasks. If the
solution turns blue, it means that not enough HCl was added. In this case, pipette an additional

67
10.0mL of HCl into the flask and boil again. Repeat these additions of HCl as necessary until
a yellow solution is obtained. Record the total volume of HCl added to each flask.
4.

Obtain about 50mL of the standardized NaOH solution in a graduated cylinder. Record the
concentration of the NaOH. If you are the first lab section of the day, rinse the clean burette
with a small portion, ~5mL, of the NaOH solution. Then, using a funnel, fill the burette. Note
that there is no reason to try to fill the burette to exactly the 0.00 mark. Make sure that
there are no air bubbles in the burette tip. Record the initial volume of NaOH (to 2 decimal
places). If you are not the first lab section of the day, there is no need to rinse the burette. Just
fill it and proceed.

5.

Make sure that the antacid solution has cooled to room temperature before proceeding. Slowly
and carefully, with constant swirling, titrate the antacid sample with the NaOH solution to a
faint blue endpoint. As the yellow colour disappears, slow down the rate of delivery of the
NaOH to a dropwise flow. When a single drop results in the formation of the blue colour,
stop! Swirl the flask for another 10-15 seconds to make sure the colour remains blue. If it
does not, add one more drop of NaOH and repeat. Read and record the final volume of NaOH
solution on the burette

6.

Titrate the contents of the second flask as in 5.

7.

Repeat Steps 1 - 6 for the other brand of antacid tablet.

8.

Unused antacid powder can be disposed of in a garbage bin. Titrated solutions can be flushed
down the sink with running tap water. If you are in the last lab section of the day, drain any
remaining NaOH that is in the burette into the sink with running tap water. Rinse the burette
twice with tap water, dispensing it through the burette tip, followed by twice with distilled
water. Clamp the burette upside down with the tip open. Rinse each volumetric pipette twice
with tap water and twice with distilled water and clamp them upside down. If you are not in

68
the last lab section of the day, leave the remaining NaOH in the burette for the students in the
next lab to use. You do not need to wash the pipette.

Calculations
1.

From the concentration of HCl and the total volume of HCl added, calculate the total number
of moles of HCl added.

2.

From the concentration of NaOH and the volume of NaOH used in the titration, calculate the
total number of moles of NaOH used in the titration.

3.

Subtracting the number of moles of base used in the titration from the total umber of moles of
acid added, gives the number of moles of acid that were neutralized by the basic antacid.
Calculate the number of moles of base in the antacid powder sample. (Dont overlook the
stoichiometry of the reaction!). Then scale this up to calculate the number of moles of base
in the whole antacid tablet. Convert the moles to grams. How closely does this number of
grams agree with the number of grams of active ingredient listed on the label of the bottle?

4.

While lay people may think that they should consider the cost per gram of the antacid, chemists
know that cost per mole of base or the cost per mole of acid that can be neutralized, is a more
meaningful measure of cost efficacy.

Calculate this cost per mole of acid that can be

neutralized.
5.

Think about what factors other than cost per mole of acid neutralized should be considered in
ones choice of an antacid.

69
Writing Assignment
This is a role playing experiment. We, the students and staff of CHM110H have been transformed into
the technical staff of GenChem Co., Ltd.*, a quality analytical chemistry testing facility. We have
been contracted by the Ministry of Health to analyze a number of commercial antacids, both for their
therapeutic and their cost efficacy. These data may be used to make decisions regarding the brands
of antacids to be routinely stocked in long-term care facilities. Therefore the writing component of
your report for this experiment is a letter to the Minister summarizing your findings and making your
recommendations. Remember, the Minister is not a chemist so your explanations must be clear in
laypersons terms. Also, the Minister is a busy person, so keep your letter to a single page.
* with permission of Prof. Peter Jeschofnig

70

71
Name:________________________

Student No.:________________

Lab Section No.:________________

Pre-lab Questions
1.

In a strong acid-strong base titration at room temperature, the pH at the equivalence point is
7. The indicator bromothymol blue changes colour over the pH range of 3.0-4.5. Explain why
it is okay to use this indicator for this titration.
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

2.

Why is it important to remove the CO2 from the solutions before doing the titration?
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

3.

The analytical technique in this experiment is referred to as back titration. Define this term.
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________
_________________________________________________________________________

72

73
Name:__________________________

Student No.:_____________________

Lab Section No.:__________________

Date:___________________________
Data Sheet

Antacid 1

Antacid 2

Identity, number
of tablets per
bottle, cost per
bottle, label
information

Sample 1
mass of weighing
paper (g)
mass of paper +
powder (g)
mass of powder
(g)
concentration of
HCl (M)
total volume of
HCl added (mL)
concentration of
NaOH (M)
initial burette
reading (mL)
final burette
reading (mL)
volume of NaOH
used (mL)

Sample 2

Sample 1

Sample 2

74

75
EXPERIMENT 4
Spectrophotometric Determination of the Stability Constant of a Complex Ion
Introduction
When a metal ion, acting as a Lewis acid, reacts with a ligand, a molecule or ion with a lone
pair of electrons and acting as a Lewis base, the resulting species is a complex or complex ion if
charged. Some common ligands are H2O, NH3, Cl- and heavier halides, CO, CN- and SCN -. Many
transition metal cations form very stable complex ions with many of these ligands and the stability of
these complex ions is expressed by the equilibrium constant for the formation of the complex ion.
Such equilibrium constants are referred to as stability constants or formation constants.
In this experiment an aqueous solution containing ferric ions is reacted with thiocyanate ion
to form a complex ion. The reaction is
[Fe(H20)6]+3(aq)

SCN-(aq)

[Fe(H20)5(SCN)]+2(aq)

H2O

Because the concentration of water in dilute aqueous solution is essentially constant, we normally omit
the waters in the equation and write a simplified version
Fe+3(aq)

SCN-(aq)

Fe(SCN)+2(aq)

for which the stability constant is expressed as

K = [Fe(SCN)+2]/[Fe+3][SCN-] .
The object of this experiment is to determine the value of this stability constant.
A knowledge of the factors influencing the stability of complex ions and knowing the value
of their stability constants is of importance in guiding the synthesis of new inorganic materials. As
well, it contributes to our understanding of many biological processes. For example, the fact that the
stability constant for the binding of CO to the Fe+2 of hemoglobin is about 250 times greater than that
for binding O2, is what is responsible for the toxicity of CO in the atmosphere.

76
Pre-lab Questions
Answer the pre-lab questions on page 81-82.
Procedure
Overview:

Known concentrations and volumes of the reactants will be mixed and the
resulting concentration of the complex ion product will be

measured

spectrophotometrically. From these data, the equilibrium concentrations of reactants

and products can be obtained and the stability constant can be calculated. This is
possible because the product has a characteristic blood-red colour while the reactants
are pale yellow and colourless respectively. Appendix B explains the relationship
between the concentration of a species and its ability to absorb light of a particular
wavelength, the Beer-Lambert Law. Appendix C explains the operation of the
spectrophotometer (colourimeter), the Spectronic 20, that will be used to measure the
absorbance of light.
In Part A of the experiment you will work with a partner to create a calibration
curve for Fe(SCN)+2, a graph of absorbance of light vs concentration of complex ion.
The solutions used to create this curve all have a very large excess of the SCN-, thus
ensuring that the reaction goes essentially to completion, i.e. that all of the Fe+3 is
turned into the complex Fe(SCN)+2.
In Part B of the experiment you will work individually. You will prepare five
different mixtures of the reactants, each containing the same amount of Fe+3 but
different amounts of SCN-. In these mixtures the concentrations of the two reactants
will be similar. So the reaction will not go to completion and an equilibrium between
reactants and products will be established. The absorbance of light of each of these
mixtures will be measured and compared with the calibration curve in order to
determine the concentration of the complex ion formed.

77
PART A (work with a partner)
1.

Turn on the spectrophotometer so that it can warm up while you prepare the solutions for
creating the calibration curve. Label six, clean and dry large test tubes, 0-5. Using the
graduated pipettes provided, prepare the six solutions as described in Table 1. Do not pipette
directly from the stock bottles of reagent. Transfer the required amount of reagent into
a clean beaker and pipette from that. Be careful not to mix up the pipettes. Each pipette
should be used for only one reagent. It is essential that there is no cross contamination
between the reagents. After all of the solutions are prepared, seal each tube with a small
square of Parafilm and thoroughly mix each solution.
Table 1. Composition of the Solutions for Preparing the Calibration Curve

2.

Solution
Number

0.1M HNO3
(mL)

0.2 M NaSCN (mL)

( in 0.1M HNO3)

0.0005M Fe(NO3)3 (mL) Total Volume

( in 0.1M HNO3 )
(mL)

0
Blank
1

10.00

5.60

4.00

0.4

10.00

5.00

4.00

10.00

4.40

4.00

1.6

10.00

3.80

4.00

2.2

10.00

3.20

4.00

2.8

10.00

Calibrate the spectrophotometer. Using the + or - button on the spectrophotometer, set the
wavelength to 447 nm. Rinse a cuvette with the blank solution, solution 0, and then fill the
cuvette up to the arrow with solution 0. Wipe the outside of the cuvette with a soft tissue to
make sure that it is clean and dry.

Place the cuvette into the sample holder of the

spectrophotometer so that the arrow is facing you. Close the cover. Press the mode button

78
to activate the abs mode and then press the set reference button to read zero absorbance.
Remove the cuvette and discard the solution in a waste beaker. Use the same cuvette
throughout the rest of the experiment. Once the spectrophotometer has been zeroed, do not
perform any reference setup for the remainder of the experiment. If you accidentally do, repeat
the calibration procedure.
3.

Measure the absorbance of the calibration solutions 1 - 5. Rinse the cuvette with solution 1
before filling it to the arrow with the solution. Wipe the outside of the cuvette, place it in the
sample holder, close the cover, and read and record the absorbance. Repeat this procedure for
solutions 2 - 5.

PART B (work individually)

1.

Before using the used pipettes, rinse them three times with distilled water and once with the
solution to be used. Label five clean and dry, large test tubes, 6-10, and prepare the test
solutions as described in Table 2 taking the same precautions as in A.1. above. After all of
the solutions are prepared, seal each tube with a small square of Parafilm and thoroughly mix
each solution.
Table 2. Composition of Test Solutions
Solution 0.1M HNO3
Number
(mL)

0.002 M NaSCN (mL)

( in 0.1M HNO3)

0.002M Fe(NO3)3 (mL)

( in 0.1M HNO3 )

Total Volume
(mL)

4.00

1.00

5.00

10.00

3.00

2.00

5.00

10.00

2.00

3.00

5.00

10.00

1.00

4.00

5.00

10.00

10

5.00

5.00

10.00

79
2. Rinse the same cuvette that was used in Part A, first with distilled water and then with solution
6. Then fill the cuvette up to the arrow with solution 6. Wipe the outside of the cuvette with a
soft tissue to make sure that it is clean and dry, place it in the sample holder so that the arrow is
facing you, close the cover and read and record the absorbance. Repeat this procedure for
solutions 7 - 10.
3. Dispose of all solutions from Parts A and B in the waste bottles in the common fumehoods.
Remove the labelling tape from all test tubes used. Rinse the test tubes with tap water and put
them in the used test tube bin. Rinse the pipets and the cuvette twice with tap water and twice
with distilled water. Ensure that your lab bench and fume hood are clean and dry.

Treatment of Data
PART A
1. Calculate the concentration of Fe+3 put into each of the solutions, 1-5. Since SCN- is in large
excess in each of the solutions, Fe+3 is the limiting reagent. So the concentration of the Fe(SCN)+2
complex formed is equal to the concentration of Fe+3 put into the solution. (See Pre-lab Question
1).
2. Plot a graph of absorbance vs concentration of Fe(SCN)+2. This is your calibration curve. You
will use it to determine the concentration of Fe(SCN)+2 in each of your test solutions in Part B.

PART B
1. Calculate the moles of Fe+3 put into each solution, 6-10, and the initial concentration of Fe+3 in
mol/L.

80
2. From the measured absorbance for each solution, read the equilibrium concentration of Fe(SCN)+2
off the calibration curve.
3. Subtracting the concentration in 2. from that in 1. gives the concentration of Fe+3 remaining at
equilibrium.
4. Calculate the moles of SCN! put into each solution, 6-10, and the initial concentration of SCN!
in mol/L.
5. Subtracting the concentration in 2. from that in 4. gives the concentration of SCN- remaining at
equilibrium.
6. From the equilibrium concentrations for each solution, 6-10, calculate the stability constant for
the reaction.
7. Calculate the average of the stability constants determined.

Writing Assignment
Assume that the spectrophotometers in the first-year chemistry lab have reached the end of their
lifetime and need to be replaced. In order for the replacement to be approved, the Dean must first be
convinced of the wisdom of this purchase. Your assignment is to write a letter to the Dean explaining
the importance of a working knowledge of spectrophotometry to practising chemists and biologists
and thereby justify the expenditure. Remember that the Dean is not a scientist; she is a professor of
philosophy.

81

Name:_____________________________

Student No.:_____________________

Lab Section No.:_____________________

Pre-lab Questions

1. The equilibrium concentration of FeSCN+2 in PART A solutions 1-5 is essentially equal to the
concentration of Fe+3 in the solution before any reaction occurs. Consider Le Chateliers Principle
and explain why this statement is true.
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
____________________________
2. According to the Beer-Lambert Law, three factors affect the absorbance of a solution. What are
these factors and which one is the focus in this experiment?
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
_____________________________
3. In this experiment the absorbance of the solutions will be determined at 447nm. Why do you
think that this wavelength was chosen? What experiments must have been done in order to select
this wavelength?

82
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
________________________________________________________________

83
Name:____________________________

Student No.:___________________

Lab Section No.:____________________

Date:_________________________

Lab Partners Name:______________________________________________________________

Data Sheet
Room Temperature:_____________
PART A
Concentration of NaSCN:_______________
Concentration of Fe(NO3)3:______________
Solution Number Absorbance
0

1
2
3
4
5

PART B
Concentration of NaSCN:_______________
Concentration of Fe(NO3)3:______________
Solution Number
6
7
8
9
10

Absorbance

84

85
EXPERIMENT 5
Measurement of the Enthalpy of Reaction by Calorimetry
Introduction
Thermodynamics is the study of energy changes when a system goes from one state to another,
e.g. a chemical reaction. Thermochemistry is the branch of thermodynamics concerned only with
heat changes.
According to the First Law of Thermodynamics although energy may be converted from one
form to another, the total energy of a system and its surroundings remains constant. Any change in
the energy content of the system is always exactly counterbalanced by an equal and opposite change
in the energy content of the surroundings.
Energy transfer between a system and its surroundings may occur by the exchange of heat, or by
the performance of work. The total internal energy content of a system is expressed by the symbol
E. When a system changes from some initial state to a final state, the change in internal energy
content may be expressed as
E = Efinal - Einitial

(1)

According to the first law of thermodynamics

E = q + w

(2)

where q is the heat gained by the system and w is the work done on the system. q has a positive
numerical value when heat is transferred to the system from the surroundings (as in an endothermic
process). It has a negative numerical value when heat is lost from the system to the surroundings
(as in an exothermic reaction).
The most usual way for work to be done on a system is in its compression by its surroundings.
Conversely, work is done by the system on its surroundings when it expands against the external

86
environment. If the volume decrease is V, and the constant pressure exerted on the system by the
surroundings is P, the work done on the system is !PV, resulting in an energy content increase in
the system by this amount. At constant pressure we can write
E = q + w = qp - PV

(3)

qp = E + PV

(3')

or

qp, the change in heat content of the system at constant pressure, is defined as its change in enthalpy,
H. Thus, we can write
H = Hfinal - Hinitial = qp = E + PV

(4)

In a liquid system, the change in volume occurring under normal conditions at constant pressure is
small, so that PV work is negligible; in this case H = E = qp, and H may be measured simply
by measuring the quantity of heat transferred from the system to its surroundings (exothermic
reaction) or from the surroundings to the system (endothermic reaction).
Some of the most commonly measured enthalpy changes include enthalpies of formation,
neutralization of an acid by a base, and dissolution of a solid in a liquid..
Since changes in enthalpy are dependent only on the initial and final states of a system, and are
therefore independent of the pathway by which these changes are carried out, equations describing
reactions leading from reactants to various products, and the corresponding standard enthalpies, may
be added or subtracted according to Hess's law to obtain standard enthalpy changes of reactions for
which these values are not readily determined by direct experimental measurements.
Calorimetry
In order to measure heats of reaction experimentally, the system must be effectively insulated
from its surroundings, so that no heat is lost from the system to the surroundings, or vice-versa. One
simple method for achieving this is to carry out the reaction in a styrofoam cup, a reasonably good

87
insulator, which makes a suitable calorimeter (Figure 1.). If the temperature change from a reaction
carried out inside the calorimeter is measured, the change in heat content may be calculated if the
total heat capacity of the system (calorimeter and contents) is known. If T is the temperature
change and Cp is the total heat capacity of the system at constant pressure
qp = CpT

(5)

where
T = Tfinal - Tinitial.
The heat capacity of the calorimeter includes that of all of its parts (e.g. the styrofoam cup, the
lid and the thermometer) and must be determined experimentally. One way of doing this is to
measure the temperature change resulting from mixing inside the calorimeter two known quantities
of water initially at different temperatures. Assuming no loss of heat from the calorimeter
* heat lost by hot water*

= * heat absorbed by * + * heat absorbed by *

cold water
calorimeter

(6)

The heat, q joules, released by the hot water can be expressed as

q = Vh CpH2O T = (heat lost by hot water)

(7)

where Vh is its volume in mL, is its density in g mL-1, CpH2O is its specific heat capacity in
J g-1 K-1, and T is the decrease in its temperature (in EK or EC). Similar expressions can be written
for the heat absorbed by the cold water when its temperature increases by TN, and for the heat
absorbed by the calorimeter. If the calorimeter and the cold water are initially at the same
temperature, the temperature rise for each is TN, and the heat absorbed by the cold water and the
calorimeter can be expressed as
q = Vc CpH2O TN + Cpcal TN
= (heat absorbed by cold water) + (heat absorbed by calorimeter)

(8)

88
where Vc is the volume of cold water in mL, is its density in g mL-1 , CpH O is its specific heat
2

capacity in Jg-1 K-1 and Cpcal is the total heat capacity of the calorimeter in J K-1. First of all you will
have to measure Cpcal and then make use of the value obtained in obtaining the heats of a number of
reactions.
For example, if you mix 10 mL of water at 22EC, with 10 mL of water at 62EC and find that
the equilibrated temperature is 42EC, then no heat was lost to the surroundings (T = T'). If the
temperature of the mixture is less than 42EC, then some heat was absorbed by the calorimeter. Its
heat capacity can be calculated from equation (8). If the temperature of the mixture is greater than
42EC, then you have managed to violate the second law of thermodynamics! Either you have made
a mistake, or you have managed to solve the world's energy problems. Of course, if the heat capacity
of the calorimeter is very close to zero, it might appear that its heat capacity is slightly negative.
Under these circumstances one considers that Cpcal = 0.
Measurement of temperature change
The calorimeter used is not a perfect insulator and heat leaks out to the surroundings, making
it difficult to measure accurately the actual temperature changes. Also, it takes a finite time for any
change in temperature to equilibrate within the calorimeter, so that all parts are at the same
temperature, and for the mercury in the thermometer to respond. To correct for these sources of
error, changes in temperature are determined graphically. This involves measuring the temperature
of the calorimeter and contents prior to mixing, and then recording the temperature of the system at
intervals of time after the time of mixing to and plotting the data as in Figure 2. Since, after mixing,
the heat leakage from the system to the surroundings is expected to occur at a relatively constant rate
(because the temperature difference system-surroundings remains approximately the same for a
reasonable length of time) a plot of temperature against time should show a linear portion after an

89
initial period required for the system to mix thoroughly and equilibrate. If this portion is
extrapolated to the temperature axis at time to, an accurate value for the temperature change can be
determined. In studying chemical reactions it is important for the mixing of two reacting solutions
to be performed very quickly. (Why?)

Figure 1. Styrofoam Cup Calorimeter

90

Figure 2. Graph of temperature versus time data for an exothermic reaction. The linear portion of
the curve, which is slowly declining after the maximum temperature has been passed because of heat
leakage out of the calorimeter, must be extrapolated back to the reaction starting time in order to
determine the temperature that would have been reached if the reaction and thermal equilibrium had
taken place instantaneously with no heat loss. The temperature change due to the reaction is T =
T2 - T1, where T2 is the high temperature extrapolated back to the staring time, and T1 is the initial
temperature.

91
In this experiment you will measure the enthalpy change for neutralization of a strong acid with a
strong base (Hneut), an exothermic process, and the enthalpy change for dissolution of a salt in water
(Hsoln).

Enthalpies of solution can be positive or negative: the dissolution process may be endothermic, with
heat being absorbed, or exothermic, with heat being evolved. If the energy of attraction of the solute
molecules or ions with each other and the energies of attraction of the solvent molecules or ions with
each other are greater than the energy of attraction of solute and solvent particles, heat will be
required to make the solute disperse in the solvent. Heat will then be absorbed in the process and the
heat of solution will be positive. In this case, the solubility of the material increases with
temperature. The heat of solution for formation of aqueous solutions of most salts is positive. The
absorption of heat as a result of a mixing process is the basis of commercial "cold-packs" used by
athletic trainers to treat minor injuries. If the energy of attraction of solute molecules or ions and
solvent molecules or ions is greater than the energies of attraction of solute particles with each other
and solvent particles with each other, heat will be released as the solute dissolves. For these
exothermic processes, the solubility decreases with an increase in temperature.* This is the basis
of commercial heat packs.
*http://www.bookrags.com/research/heat-of-solution-woc

Pre-lab Questions
Answer the pre-lab questions on pages 97-98.

92
PART A - Heat Capacity of the Calorimeter
Procedure
1.

With a graduated cylinder, measure out 50 mL of distilled water at room temperature.

Transfer it to the clean dry calorimeter, which is fitted with a special thermometer calibrated
to 0.1EC. Stir carefully with the thermometer and allow to stand until the temperature
reading remains constant.

2.

Take 50 mL of distilled water from the high temperature water bath (~40EC). Measure the
exact temperature and immediately transfer it to the calorimeter, as quickly and completely
as possible. Begin measuring the time when all of the water has been added, and note the
time and temperature at 15 sec intervals from then on for 4 minutes. Stir constantly both
during and after the addition of the hot water.

Calculations
1.

Plot a temperature versus time graph and determine the temperature at the instant of mixing
by extrapolation. What does the plot tell you about the effectiveness of the styrofoam cup
as an insulator?

2.

Calculate the heat capacity of the calorimeter, using equation (6),assuming that the specific
heat capacity of water is 4.18 J g-1 K-1 and that the density of the water is 1.00 g mL-1.

PART B - Enthalpy of Neutralization of a Stong Acid

The heat of neutralization of a strong acid, hydrochloric acid, will be determined. The strong base
is sodium hydroxide of a concentration slightly less than that of the acid.

93
Procedure
1.

In a clean dry graduated cylinder, measure out exactly 50 mL of the NaOH solution and
transfer completely to the clean dry calorimeter.

Record this temperature and the

concentration of the NaOH solution.

2.

Meanwhile, rinse out the graduated cylinder with tap water, distilled water and a few mL of
the HCl solution. Measure out 50 mL of the HCl solution. Allow it to stand until its
temperature is constant and equal to room temperature. Record this temperature and the
concentration of the acid solution.

3.

Add the acid as quickly as possible to the calorimeter, counting the time from the addition
of the first drop of acid. Note the time and temperature after the addition of the last drop, and
at 15 sec intervals from then on for 4 minutes. Stir the contents of the calorimeter constantly.

4.

Test the contents of the calorimeter with litmus paper. The solution should be slightly acidic
(pH<7.0), indicating that the known amount of base was completely consumed in the
neutralization.

Calculations
1.

Plot a temperature versus time graph. Extrapolate the linear portion to zero time. From the
intersection with the temperature axis at zero time, calculate the temperature changes T and
TN for the acid and base, respectively.

2.

Calculate the total heat, qp, released in the neutralization (the heat gained by the acid plus the
heat gained by the base plus the heat gained by the calorimeter). Assume that the heat
capacities of both the acid and base solutions are equal to that of water, 4.18 J g-1 K-1, and
that the density of each of the solutions is 1.00 g mL-1.

3.

Calculate the number of moles of acid neutralized.

94
4.

Calculate the enthalpy of neutralization of HC1 in kJ mol-1. Is the reaction exothermic or

endothermic? What is the accepted literature value for the molar enthalpy change in this
reaction. Comment on any difference between your value and the literature value.

PART C - Enthalpy of Solution of a Salt in Water

Procedure
1.

With a graduated cylinder, measure out 50 mL of distilled water at room temperature.

Transfer it to the clean dry calorimeter. Stir carefully with the thermometer and allow to
stand until the temperature reading remains constant.

2.

Weigh out approximately 5g of ammonium chloride (mass must be accurately known).

3.

Add the salt as quickly and completely as possible to the calorimeter, counting the time from
the addition of the salt. Replace the lid. Stir the solution constantly. Note the time and
temperature at 15 sec intervals for about 4 minutes.

4.

Repeat steps 1 - 3 using sodium acetate as the salt.

5.

Rinse the coffee cups twice with tap water and twice with distilled water. Dry.

Calculations
1.

Plot a temperature versus time graph. Extrapolate the linear portion to zero time. From the
intersection with the temperature axis at zero time, calculate the temperature change, T..

2.

Calculate the total heat qp absorbed or released in the dissolution (the heat change for the
water plus the heat change for the salt plus the heat change for the calorimeter).

3.

Calculate the number of moles of salt dissolved.

95
4.

Calculate the enthalpy of solution of the salt in kJ mol-1. Is the reaction exothermic or
endothermic? What is the accepted literature value for the molar enthalpy change in this
reaction. Comment on any difference between your result and the literature value.

96

97
Name:

Student No.:

Lab Section No.:

Pre-lab Questions

1.

50 mL of water at 46.9EC were mixed with 50 mL of water at 25.1EC in a calorimeter also

at 25.1EC. The final temperature was 30.1EC. Assuming that neither the density of water
nor its specific heat capacity change with temperature, calculate the total heat capacity of the
calorimeter.
(density of water = 1.00 g mL-1, specific heat capacity = 4.18 J g-1 K-1)

98
2.

Suppose that you repeated PART B of the experiment using 1 M HNO3(aq). How would you
expect the Hneut to compare with that for the neutralization of HCl? Explain.
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

3.

As a result of a manufacturing error, a thermometer was miscalibrated by 2EC over the entire
thermometer scale. If this thermometer was used in PART B of this experiment, would it
cause the determined Hneut to be higher, lower or the same as it would be had a properly
calibrated thermometer been used? Explain.
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

99
Name:

Student No.:

Lab Section No.:

Date:
Data Sheet

PART A - Heat Capacity of the Calorimeter

volume (mL)

initial temperature (oC)

hot water:
cold water:

temperature of mixture (oC)

time after mixing (s)

100
PART B - Enthalpy of Neutralization of Strong Acid
concentration (M)

initial temperature (oC)

volume (mL)

strong acid (HCl):

strong base (NaOH):
____________________

temperature of mixture (0C)

time after mixing (s)

101
PART C - Enthalpy of Solution of a Salt
mass of NH4Cl (g):________________

mass of NaA (g):____________________

volume H2O (mL):________________

volume H2O (mL):__________________

initial temperature (oC):_____________

initial temperature (oC):______________

temp. of mixture (oC) time after mixing (s)

temp. of mixture (EC) time after mixing (s)

102

103
Appendix A

ERROR ANALYSIS

Many of the experiments that we carry out are concerned with the quantitative determination
of some quantity, such as mass, concentration, volume, temperature, etc. The measuring devices
(instruments) that we use are themselves calibrated in suitable units but errors are introduced
inevitably into results as a result of the imperfection of this calibration.

Values for accuracy

tolerances of various items of equipment we use are given at the end of the Appendix. Not only
does the imperfection of calibration introduce errors but so does the accuracy with which we can
read the instrument. For example, in using a buret to measure a volume, the interval between the
graduations is 0.1 mL and if we interpolate between graduations it is possible to estimate the volume
only to 0.02 mL with any certainty. Similarly, if we measure a temperature and the graduations are
at 1EC intervals, it is possible only to read the temperature to 0.5EC. We have, therefore, to be
always aware of the limitations of our measuring devices and take into account the experimental
uncertainty that they inevitably introduce. We refer to such errors as instrumental errors.
Error in an experiment may also be introduced either through the experimenter's lack of skill
or carelessness. Avoidable errors include factors such as the misreading of scales or loss of materials
from an experiment, either through spills or because the apparatus is dirty -- a dirty pipet will not
deliver its stated volume of solution. Such errors are referred to as personal errors.
A third source of error is method error which is inherent to the procedure used. How we
design the experiment imposes a limit upon the degree of experimental accuracy possible so that

104
results cannot be improved beyond this limit, regardless of the care with which the experiment is
performed.
Personal errors can be avoided if the experimenter is skilled and careful. If an experiment
is repeated several times using exactly the same procedure, we expect to obtain the same value. The
internal agreement within such a set of experimental values is referred to as their precision. The
error is the difference between your experimental result and the accepted best or 'true' value.
If we can identify the contributing sources of error, and their magnitude, application of the
rules below enables the experimenter to calculate the error expected in the final result. This error,
as well as the precision, should be quoted together with the final value.
A. Propagation of errors
Rules about the propagation of errors may be deduced from the principles of statistics. Those
pertinent to this course are given below. Note that there exists two equally popular methods of
expressing error: it may be referred to as the 'absolute error', a value with the same units as the
quantity to which it applies, or as the 'relative error', which is obtained from the ratio of the
absolute error to the quantity in which the error is being calculated. When a measurement is being
made -- usually by reading a scale -- the absolute uncertainty in the measurement is often estimated
to be one-half of the smallest scale division.
Rule 1 Addition or subtraction of quantities e.g. z = x+y or z = x-y
When x and y are measured quantities for which the absolute uncertainties are x and y,
respectively, the error in z is given by

Rule 2 Multiplication or division of quantities e.g. z = xy or z = x/y

The relative uncertainty in z is

105

where x/x and y/y are the relative uncertainties in x and y.

Rule 3 Raising a quantity to a fractional or integral power n e.g. z = xn

Rule 4 Logarithms
When the result being calculated is obtained through a logarithmic relationship,
e.g. z = log x.
The absolute error in z, z, is given by:

B. Tolerance Errors
In the calculation of experimental error, the limits imposed on the accuracy by the tolerances of
calibrated laboratory equipment should be added to the reading error. The tolerances for some items
of laboratory ware are givenin the table below:

106
tolerance *

equipment
buret - 50 mL

0.02 mL

pipet - 5 mL

0.01 mL

10 mL

0.02 mL

25 mL

0.03 mL

volumetric flask - 100 mL

0.08 mL

250 mL

0.12 mL

500 mL

0.15 mL

analytical balance

0.0001 g
* or as printed on the equipment

C. Importance of Significant Figures

See pages 24 - 29 in your textbook.
D. Example of Error Calculation
The molarity (mol L-1) of a sodium hydroxide solution was determined by titrating a sample
of the strong acid potassium hydrogenphthalate with the base NaOH. Potassium hydrogenphthalate
is used as a standard because it can be obtained as a pure solid that readily dissolves in distilled
water. The results obtained in one such titration were:
mass of potassium hydrogenphthalate = 0.2631 g
volume of NaOH required to reach the end point = 27.93 mL
(gram molar mass of potassium hydrogenphthalate = 204.22 g)
1. Calculation

number of moles of potassium hydrogen phthalate titrated =

0.2631 g / 204.22 g mol-1

107
concentration of NaOH solution =

0.2631
g
______________
204.22 g mol-1

1________

27.93 mL

1000
mL
________
1L

4.613 x 10-2 mol L-1 (to 4 sig figs)

2. Error analysis
The mass of potassium hydrogen phthalate was found from two weighings -- the mass of
the solid + weighing bottle minus the mass of the weighing bottle. Each mass was uncertain
to 0.0001 g (the accuracy with which the scale could be read). By applying Rule 1, the
error in sample mass is 0.0001 g which, when it is added to the accuracy tolerance of the
balance, becomes 0.0002 g.
Similarly, the titration volume was obtained by taking two readings -- one before the
titration and one at the end-point. The readings were each accurate to 0.02 mL, which when
combined according to Rule 1 give an error of 0.03 mL. This error becomes 0.05 mL
once the tolerance of the buret calibration is taken into account.
Since the molarity is calculated by division of the mass of potassium hydrogen phthalate
by the titration volume, rule 2 must be applied to give the combined error:

This corresponds to an absolute error of 0.00009 mol L-1 (0.2% of 0.046 M) and the
molarity of NaOH is quoted as 0.04613 0.00009 mol L-1

108
If three separate titrations were performed, for which the results were found to be:
run 1: 0.04613 0.00009 mol L-1
run 2: 0.04618 0.00009 mol L-1
run 3: 0.04620 0.00009 mol L-1
then the mean value of the molarity is (0.04613 + 0.04618 + 0.04620)/3 = 0.04617 M. The absolute
uncertainty in the mean is obtained by dividing the absolute uncertainty in any one of the values
(0.00009 mol L-1) by the square root of the number of values considered in calculating the mean.
In this example this is (9 x 10-5)//3, or 5 x 10-5 mol L-1
Mean NaOH molarity = 0.04617 0.00005 mol L-1

3.

Precision
To illustrate the calculation of precision as applied to this example, consider the definition

precision =

sum of the absolute value of

the deviation of each result
from the mean
(number of results) x (mean value)

x 100%

Notice that the absolute deviation of each value is included in the sum -- that is, each difference is
assumed to have a positive sign. For this example

4.

Accuracy
In cases where there is a known or literature value for the parameter being measured, the
accuracy of the experimental value can be expressed by calculating the percentage deviation
of the experimental value from the literature value.

109
% deviation =

* experimental value - literature value* x 100

literature value

So, for example, if one experimentally determined the atomic mass of Zn to be 64.12, the %
deviation would be * 64.12 - 65.39 * x 100 = 1.94%
65.39

E. Uncertainty in the Slope of a Straight Line

When a calculation is based on the slope m, of a straight-line plot, y = mx + b, the simplest approach
is visually to estimate the uncertainty of the slope as follows.
1. Plot the points and draw the straight line which passes closest to most of them (slope m).
2.

Calculate uncertainties in the x and y

parameters for each point and plot them as

error bars.
3.

Draw two new lines with slopes as

different as possible, one higher, one lower,

than the first line, but passing through error
bars of all points (slopes m1, m2).
4. The uncertainty in the slope is then

Note: Calculating uncertainties for every point can be time-consuming. It is usually adequate to
calculate uncertainties for the points at the beginning and end of the line and to estimate the others.

110
Appendix B
BEER-LAMBERT LAW

The concentration of a coloured constituent can be determined by measurement of the relative

intensity of a light beam before and after passage through a solution. Io is the intensity of the
transmitted light (Io > It) and R is the length of the path of the light through the solution.

The laws describing this absorption can be readily formulated. The first law relates the
intensity of the light to the path length when working with a fixed concentration of the coloured
constituent. It is evident that if radiation with intensity I passes through a thin layer of the solution
and is partly absorbed, the intensity of the radiation entering the next thin layer of solution will be
less and will in turn be decreased by the next thin layer of solution. The cumulative effect can be
expressed as

- dI / dl

or

- dI / dl

k1 I

111
The constant k1 depends on the wavelength of the radiation and on both the nature and concentration
of the coloured substance. Rearrangement, followed by integration, gives

It
I - dI / I
Io

t
I

k1 dl

or

ln (It / Io)

- k1 l

This is often called Lambert's law, and there are no known deviations from this law with
homogeneous materials.
The second law relates the intensity of the light to the concentration of the coloured constituent
when working with a fixed path length. The effect is expressed by the equation

- dI / dc

or

- dI /dc

k2 I

Here the constant k2 depends on the wavelength of the radiation, the path length, and the nature of
the coloured substance. Rearrangement, followed by integration, gives
It
I - dI / I
Io

cx
=

k2 dcx

or

ln (It / Io)

- k2 cx

This is known as Beer's law. If a solution is sufficiently dilute, the law is obeyed exactly for
monochromatic light; however, some systems do show deviations as the concentration is increased.
These deviations come about as the coloured ions or molecules come closer and closer together and
modify each other's light-absorbing characteristics. There are also apparent deviations when the
coloured constituent is involved in a chemical equilibrium.
If the solution is diluted, the equilibrium shifts and the decrease in concentration of the
coloured constituent (Fe(SCN)2+(aq) is not proportional to the dilution.
If both relations (1) and (2) are obeyed, then

112
ln (It / Io)

-kN l cx

or

log (It / Io)

-k l cx

where k is a constant depending on the wavelength of the radiation and the nature of the absorbing
species. It is convenient to define the absorbance (A) of the solution such that

- log (It / Io)

k l cx

The absorbance is an experimentally measured quantity and it is directly proportional to

concentration. The concentration can be expressed in any convenient units, (that is, grams per litre,
molarity, and so forth), but the value of k will depend upon the units chosen for cx. If the
concentration is expressed in moles per litre and the path length in centimetres, then the constant is
given the special symbol g(epsilon) and is known as the molar absorptivity constant:
A

l cx

Absorbance Measurements
The absorbance of a solution can be determined by eye, relative to some visual scale, but absorbance
measurements are more accurately made by using a spectrophotometer. (The operation of the
Bausch and Lomb Spectronic 20 colorimeter is discussed in the Appendix D).
The usual instrument employs a tungsten lamp and a grating or prism monochromator to give
light of the wavelength desired for the measurement. The measurement involves two steps:
1.

Filling the cell with a reference blank solution and adjusting the instrument so that it reads 100
percent transmittance (zero percent absorption).

2.

Filling the cell with the unknown solution containing the coloured substance and again reading
the percent transmittance (<100 percent, light is absorbed). The percent transmittance
corresponds to

113
Percent T

(It / Io) x 100

so that absorbance

- log (It / Io)

Absorbance (A) = optical density (O.D.)

- log ( Percent T / 100)

k l cx

114
Appendix C
SPECTRONIC 20

The Spectronic 20 is a small single-beam spectrophotometer to measure light absorption in

liquid samples. The wavelength is set manually and each absorbance reading is read from a meter.
The standard model measures absorbance in the 400 to 625 nm region. The addition of a red filter
and a red-sensitive phototube allows measurements to be made in the 625 to 950 nm region.

The arrangement for measuring the light transmission properties of solutions is represented in
the figure. Polychromatic radiation from a tungsten lamp is focussed on a diffraction grating that
separates the white light into various wavelengths. The diffraction grating is rotated by the
wavelength-control knob so that the desired wavelength passes through the exit slit.
The light control is a gate that is adjusted by the light-control knob to regulate the amount of
light falling on a solvent blank so that the meter reads 100% transmittance. The meter is calibrated
in this way so that the unknown sample is compared directly with the blank.
After passing through the exit slit the light beam enters the sample contained in a
spectrophotometer cell. The transmitted light that is not absorbed by the sample is detected at the
measuring phototube where it is converted to an electrical signal. The electrical energy is registered
on the scale which is calibrated to measure absorbance (unitless) and percent transmittance.

115
Whenever the cell is not in the sample holder, a trip lever drops an occluder in front of the light
beam so that the meter should read zero percent transmittance or infinite absorbance. The meter is
calibrated by adjusting the scale to this reading using the zero-adjust knob.
The purpose of the reference phototube is to monitor the tungsten lamp output in order to
maintain a constant light intensity output. A bridge circuit compares the reference phototube output
with the voltage from the power supply (wall). Fluctuations in voltage supply to the lamp are
cancelled out by means of an electronic circuit. The result is a constant light intensity from the lamp.

Operation of the Bausch and Lomb Spectronic 20 Colorimeter

Matched 1/2 inch diameter cells are provided for the spectrophotometric measurements. These
are to be handled with care. To avoid scratching the optical surfaces, never bring them into contact
with a hard surface. If it is necessary to clean the cells, use soap solution, rinse with distilled water,
and dry the outside with soft, lint-free absorbent tissue. Rinse two or three times with the sample
before using. Note the index mark provided on the circular cells. This allows reproducible
positioning so that the light beam always passes through the same part of the cell.

116
To operate perform the following operations in sequence.
1.

The left-hand front knob is the "on-off" switch and zero-adjust knob. The instrument should
be warmed up for 30 minutes before use.

2.

Select the wavelength for the spectrophotometric measurement; this is done with wavelengthcontrol knob at the top right.

3.

With the cell compartment empty and closed, set the zero-adjust so that the meter reads "O" on
the transmittance scale ("4" on the absorbance scale). There should be negligible drift of the
meter on this setting. The meter should be read by lining up the needle with its reflection in the
mirror behind it. This makes certain that your eye is always directly in front of the needle when
you read the meter.

4.

Fill a cell with the reference "blank" solution and insert it in the cell compartment. Insertion
of the cell opens the shutter (sharp click) and permits light of the selected wave-length to pass
through the solution and strike the photocell. Cover the cell compartment to exclude stray light
from the photocell. Adjust the light-control knob on the right front so that the meter reads "100"
on the percent transmittance scale ("0" on the absorbance scale).

5.

Remove the reference "blank" and replace it with the matched cell containing the sample
solution. Cover the cell compartment to exclude stray light from the photocell. Read and
record the absorbance (lower scale) of the sample.

6.

Repeat operation 4 for each wavelength used.