CHM 120H5Y

Chemical Principles 2
2020-summer

COURSE MANUAL
______________________________
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Erindale College
University of Toronto Mississauga
 NOTICE TO ALL CHEMISTRY STUDENTS

All students working in the Chemistry undergraduate laboratories MUST WEAR INDIRECTLY-
VENTED 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 6

Lecture and Test Schedule 7

Laboratory and Tutorial Schedule 8

Textbook Assignments (for practice) 9

Additional Problems - Unit 2 - Organic Synthesis 10

Lecture Note Supplement - Unit 1 - VSEPR Theory 11

Marking Scheme 13

Policies Regarding Work Not Done or Submitted Late 13

General Laboratory Instructions 14

Materials 16

Safety 16

Laboratory Practice 17

The Laboratory Notebook 19

The Report 20

Laboratory Report Marking Scheme 21

Integrity and Ethics in the Laboratory 22

Experiments

1. Mass Spectrometry 23

2. Qualitative Analysis of Cations 31

 3. Measurement of the Enthalpy of Reaction by Calorimetry 41

4. Determination of a Molar Mass by Freezing Point Depression 52

5. Determination of the K¬sp and Standard Thermodynamic

Parameters for Dissolving Ca(OH)2

Appendices

A. Error Analysis 66

B. Beer-Lambert Law 74

C. Spectronic 20 78
 CHM 120H5Y
Chemical Principles 2

2020 Summer

Welcome to CHM120H. I hope that through this course you will come to appreciate chemistry at
the microscopic level and will see how we develop explanations for our macroscopic observations.
I look forward to working with each of you, to advising on your programs in the sciences, and to
mentoring you as you progress towards your goals.

Instructor: Thottackad Radhakrishnan

Room: 4059E, Davis Building
Phone: (905) 828-5358
E-mail: [email protected]
Office Hours :
Mon & Fri 10:00-11:00 a.m.

Lecture
Times:
Mon,Th, F 11-1 pm

Texts: S. Zumdahl and D. DeCoste, “Chemical Principles, 8th Edition,” Brooks/

Cole Cengage Learning (2016) - with Students Solutions Manual and
OWL

CHM120H Course Manual, available on the CHM120H Blackboard

website

Other
Required
Materials:

1. 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 2020-Summer

Starting Unit Number

Date of Chapter Topic
Lectures

3 11 Electrochemistry
July 6

12, 13 and parts of Atomic structure, Molecular

1 17 14, parts of 16 Structure States of Matter and

Intermolecular Forces
and 17

July 30 2 9 21 and lecture notes Organic Chemistry, Green Chemistry

Aug 10 3 6 15 Kinetics

Thursday, July 23, 11:00-12:00 noon

Mid-term Test: Thursday, Aug 6, 11:00-12:00 noon

Final Exam: Sometime in the period of Aug 19-21, online exam' Ttime to be

determined

N.B.: check the deadline to drop thecourse without academic penalty.

 CHM120H5S Laboratory and Tutorial Schedule – 2020 Summer

Week of Practical/Tutor Experiment Reports

ial Due
July 6 Tutorial
July 13 Tutorial Quiz 1

July 13 Practical Exp 1- Mass Spectrometry

July 20 Tutorial Quiz 2
July 20 Practical Exp 2- Qualitative Analysis of Cations Exp 1

July 27 Tutorial Quiz 3

July 27 Practical Exp 3 Measurement of the Enthalpy of Exp 2
Reaction by Calorimetry
August 3 Tutorial Quiz 4
August 3 Practical Exp4- Determination of a Molar Mass by Exp 3
Freezing Point Depression

August 10 Tutorial Quiz 5 Exp 4

August 10 Practical Exp5- Determination of the Ksp and Standard TBA
Thermodynamic Parameters for Dissolving
Ca(OH)2

Midterm Test 1, July 23, 11am

Midterm Test2, August 6, 11am
All lab reports must be submitted on Quercus.
Note that lab reports are due in the weeks noted above. Please write on the
cover page of the report: (1) due date for submission (2) actual date of
submission.
There will be a late penalty of 5 marks off the lab report mark per calendar day to a
maximum of 7 days, after which a mark of zero will be given.
 Textbook Assignments (for practice)
The following Chapters will be studied (specific pages are listed below).
Electrochmistry: 11
Unit 1 - Atomic and Molecular Structure: 12, 13 and parts of 14, 16 and 17 (plus notes on
pages 6-7 of this manual)
Unit 2 - Organic Chemistry: 21 (plus lecture notes)
Unit 3 - Kinetics: 15
The reading and problem assignments are listed below. The assigned problems are to guide you in
your study. They will be discussed in your tutorials. The assignments are not to be handed in,
however their content will be reflected in the quizzes.
Chapter 11
Reading sections - 1-4 . Problems 1-9, 15-71 odd,

Chapter 12 UNIT 1
Reading: 1-13 and 15-16
Problems: 1-9, 21-53 odd, 63-75 odd, 76, 77-127 odd, 131,135
Chapter 13
Reading: All sections
Problems: 1, 4, 6-8, 13-55 odd, 6, 63, 67-111 odd, 119, 120, 135, 137
Chapter 14
Reading: Sections 1 and 6 only.
Problems: 5, 6, 8, 9-33 odd, 65, 67, 71
Chapter 16
Reading: Sections 1,2 and 10
Problems: 2, 4, 7, 9, 11-19 odd, 27, 29, 8, 83, 85, 90
Chapter 17
Reading: Sections 4-7
Problems: 6, 9, 43,45, 49, 58, 59-91 odd, 135

UNIT 2
Chapter 21
Reading: All sections
Problems: 1-155 odd plus problems on page 5 of this manual

UNIT 3
Chapter 15
Reading: All Sections
Problems: 1-4, 7, 11-25 odd, 28, 29-55 odd, 56, 57-95 odd, 128.
 Additional Problems - Unit 2
Organic Synthesis

1. Show how butan-2-one can be synthesized from ethanol and inorganic reagents.

2. Show how to prepare 1, 2-dibromo-2-methylpropane from propan-2-ol and methyl bromide.

3. How could methylcyclopentane be most efficiently synthesized (fewest number of steps)

from cyclopentanone and any other organic and inorganic reagents?
 Lecture Note Supplement - Unit 1
Valence Shell Electron Pair Repulsion Theory

VSEPR Theory is used to explain the observed shapes of molecules and complex ions and to predict

the shapes of species for which experimental data is not available. This theory is based on the

assumption that the most stable structure for a species will be that in which the repulsions between

electron pairs is minimized. In predicting the shape of a species, these steps are usually followed.

1. Draw the Lewis structure of the species.

2. Classify the species according to the AXmEn nomenclature of the VSEPR Theory and

determine the steric number of the central atom, n+m (where A represents the central atom;

X, the atoms or groups of atoms bound to A (the ligands); and E, the lone pairs of electrons

associated with A).

3. The steric number gives the total number of lone pairs and sigma bonding pairs of electrons

that surround the central atom. Distribute these pairs of electrons around the central atom

in a regular geometrical shape that will maximize the distance between the electron pairs and

therefore minimize the electron pair repulsions.

4. If the electron pairs are not all equivalent, i.e. if there is a mixture of lone pairs and bonding

pairs or if there are bonds to different atoms or groups of atoms, distort the regular geometry

in order to take account of the different attractions of electron pairs to nuclei.

This method is very effective for simple species such as CH4 or H3O+. However, for more complex

species the first step, drawing the Lewis structure can be time consuming and the greater the number

of electrons in the species, the greater the chance of making an error in the Lewis structure. For such

species, another procedure might be followed.

1. a. Count all of the valence shell electrons of the central atom, A.

b. Add electrons from the ligands according to this formula.

If the ligand has add

8 electrons 2 electrons

7 or 1 1

6 0

5 -1

4 -2

c. Compensate for any ionic charge by adding electrons for negative ions and

subtracting electrons for positive ions.

2. Divide the total number of electrons from 1.(a. - c.) by 2 to get the steric number of the

central atom, A. Then proceed with steps 3. and 4. of the method above.

To illustrate this second method, consider the complex ion, HCO3-. The central atom, C, has 4

valence shell electrons. It is attached to an OH group which has 7 electrons, so count 1; it is also

attached to two O s, each of which has 6 electrons so count none. For the negative charge, add 1

more electron. The total number of electrons is then 4 + 1 + 0 + 0 + l or 6 so the steric number is

3. All 3 pairs of electrons must be used for bonding so there are no lone pairs; the formula is AX3

and the shape of the molecule around the C is expected to be trigonal planar. Now consider the

molecule, SOCl2. Count 6 electrons for the central atom, S, none for the O and 1 for each of the Cl

s giving a total of 8 electrons or a steric number of 4. Since there are only 3 things to bind to the S,

there must be one lone pair of electrons associated with the S. The formula is AX3E and the

molecule is expected to have a trigonal pyramidal structure.

 Marking Scheme
Experiments: (4% each) 20
Quizzes (2% each) 10

15
1 Hour Test - July 23, 2019
15
1 Hour Test - August 6, 2019
35
Final Exam - TBA, August 19-21, 2019

Participation 5
Total All marks represent % of Total mark. 100

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 student’s 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. Declare your absence on ACORN and send a screenshot of your
declaration to the instructor. Documentation appropriate to the reason for the absence
should be attached to your 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. The penalty for late submission of a laboratory report is 5 marks off per calendar day to
a maximum of 7 days, after which a mark of zero will be given.

3. Final Examination: Refer to the UTM Academic Calendar for these regulations.
General Laboratory Instructions
(You are not practicing all these instructions as you dont have in-person labs.
However, these are included here for your information)

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.”

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.”

1. Materials

a. This Course Manual/Notebook must be brought to all laboratory classes.

b. A laboratory coat (100 % cotton recommended) to protect you and your ordinary

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
 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
 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) Never return unused chemicals to the stock reagent bottles

b. 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
 plate or a hot water bath on a hot plate should be used. There should be no

open flames in the laboratory.

(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.

The Laboratory Notebook

Laboratory work may not be done without this Manual (used also as a Notebook).
4. 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.[while watching the video of the experiment during the lab period, you must

write down all observations and readings and submit it to your TA at the end of the

lab period (this process will replace signing the data sheet by your TA at the end of

the lab in in-person labs. This will be evaluated by your TA.

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

pre-lab questions for the experiment. Pre-Lab Questions must be submitted on

quercus before the lab period begins. Late submissions will not be accepted.

c. you
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 . Trying to remember afterwards

or jotting down observations on scraps of paper is unreliable and represents poor

 laboratory technique.

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

5. 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 TA’s 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 as Introductio/Purpose giving a brief account of the background ,

importance and goal of the experiment. Give chemical equations where applicable;

the Experimental Method - the actual record of how the experiment was done,
c.
taken from your notebook record. Deviations from the procedure given in the lab

manual should be described in detail. The instructions in this manual should not

be mindlessly rewritten in your report. Therefore this section should be very

brief unless there were significant deviations from the procedure in the Course
Manual. Give reference to lab 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, mostly

errors inherent in the method, or suggestions for improvements of the experiment;

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

appropriate);

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

(1) books
Author Title ; Publisher : Place
Zumdahl, S. Chemical Principles, 6th edition; Brooks/Cole: Belmont,CA;

Year Page
2009; p 47

(2) journals
Author Journal Year, Vol., Page

Aggarwal, V.A. J. Am. Chem. Soc. 1996, 118, 7004

(3) websites
last
Author Title URL update
Hsu, D. Chemicool Periodic Table ; http://www.chemicool.com; Aug. 5,

date of access
2011; accessed on June 5, 2012

g.

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.

6. 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. 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 -3
permanent ink
not reading
not bringing lab coat -2 equipment to its -3
tolerance level
leaving a mess -2 (for everyone in leaving a dirty
around the balances the section) workstation at the -2
end of the lab period
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 don’t
have goggles, you will not be allowed in the lab.
**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.

7. Integrity and Ethics in the Laboratory

“A scientist’s 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

can. In CHM120H 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.
 Experiment 1
MASS SPECTROMETRY

Introduction
Mass spectrometry is a technique used to confirm or identify chemical species. The
instrument used in mass spectrometry is known as a mass spectrometer. It is designed to ionize
gaseous molecules, separate the ions produced on the basis of their mass-to-charge ratio and
record the relative number of different ions produced. A plot of the relative number of ions of
relative intensity versus the mass/charge ratio (m/q) is known as a mass spectrum. Mass
spectrometry has a widespread number of applications in all branches of chemistry as well as in
physics, geology, astronomy, biochemistry, medicine and ecology. A number of these
applications are illustrated at the end of this write-up.
The first mass spectrometer was developed in 1911 by J. J. Thompson, at Cambridge.
Thompson discovered, in a mixture of noble gases, the presence of isotopes of neon, 20Ne and
22
Ne. Isotopes are chemically indistinguishable because they have the same number of protons
and electrons. They are, however, physically distinguishable since they contain different numbers
of neutrons, giving rise to different atomic masses. As we will see later, isotopes play an
important role in the identification of an unknown sample.
A number of different types of mass spectrometers are available for use. Low resolution
spectrometers are the more common type used in teaching or analytical laboratories, and can
separate two ions differing in mass by one unit (i.e. 85 to 86). High resolution spectrometers can
separate two ions differing in mass by one part in ten thousand (i.e. 499.95 to 500.00) with
enough accuracy to positively determine the atomic composition of the compound, and are found
mainly in research laboratories or in analytical applications demanding very high resolution.
Although the mass spectrometer is a highly complicated instrument, it's operation is
relatively easy to understand. Fig. 1 shows a typical low resolution 180E deflection mass
spectrometer.
 Fig. 1. A Schematic Diagram of a Low Resolution 180E Deflection Spectrometer.

The following will describe the electron impact method of ionizing gaseous molecules. In

this method, the sample is ionized through collisions with electrons. The sample to be analyzed is

injected into the spectrometer through the sample inlet system. Mass spectra are run in the

gaseous phase; if the sample is a liquid or a solid, it is heated and vaporized to the appropriate

pressure (about 10-4 Torr). The gas beam then passes into the ionization region. Here, a filament

is heated, producing a beam of electrons with which the gas beam collides to form ions. These

ions then pass into the acceleration region, where they are accelerated by passing through two

plates with a large potential difference (a few thousand volts) between them. The ions are

accelerated by this potential according to

 ½ mv2 = qV (1)

where m is the mass of the ion in kg, q the charge in coulombs, V the potential of the ion

accelerating plate in volts, and v the velocity of the particle in m/s. The accelerated ions now pass

into a magnetic field B (measured in tesla), where they are deflected along a circular path given by

r = mv/qB (2)

where r is the radius of the path in m. Eliminating v from these two equations gives

m/q = B2 r2 / 2 V (3)

Equation (3) gives m/q in units of kg/C. For the purposes of this lab, we would like the

mass/charge ratio to be in units of (atomic mass units)/(number of electron charges), M / Z.

q = Ze where Z is the number of electron charges and e is the charge per electron,

1.602 x 10-19 C/electron

m = (1.673 x 10-27 kg/amu) M where M is the mass in amu

Thus we need a scale factor of (charge on electron in C)/(mass of proton in kg). Hence

M/Z = (B2 r2 / 2 V)(1.602 x 10-19/1.673 x 10-27) (4)

Henceforth, we will assume the mass/charge ration, M / Z, to be in units of amu/electron charge.

This equation tells us that only ions with a given mass/charge ratio will arrive at the

detector placed at the exit of the fixed path r. Furthermore, by varying either the magnetic field B

(in the range of 0T-0.8T) or the accelerating voltage V (in the range of 0V-2000V), it is possible

to scan all values of m/q to obtain a spectrum of the ions. It is generally assumed that the majority

of the ions are singly charged, ions of higher charge being produced in insignificant quantities.

After passing through the magnetic field, the accelerated ions enter the detector, and the relative

amount of each ion is recorded.

Let us now say a few words about interpreting the data collected by the mass spectrometer.

There are a number of different reactions which can occur in the ionization region of the

instrument. Consider the molecule ABC. It can undergo any of the following reactions:
 (R1) ABC + e- 6 ABC+ + 2e-

(R2) ABC + e- 6 AB+ + C + 2e-

(R3) ABC + e- 6 AC+ + B + 2e-

(R4) ABC + ABC+ 6 (ABC)2+ 6 BC + ABCA+

In reaction 1, the molecule loses one electron to form what is known as the parent molecular ion.

In the mass spectrum of a sample, the peak due to this ion (the molecular ion peak) is very

important, since the mass (strictly M / Z, but we assume Z = 1) at which this peak occurs is the

molecular weight of the sample. Hence, proper identification of the molecular ion peak is very

important in identifying an unknown compound. The particle of highest M / Z in the mass

spectrum generally corresponds to the parent molecular ion. N.B. In some cases, particularly in

compounds containing chlorine, a parent molecular ion peak does not appear in the spectrum. In

these cases the peak with the highest M / Z that is observed corresponds to a fragment from which

chlorine has already been lost.

Many of the molecular ions formed by reaction 1 disintegrate to give a charged fragment

and a radical. This is shown by Reaction 2, referred to as fragmentation. These fragments can,

in turn, break apart to form new fragments. Reaction 3 illustrates that fragmentation may be

accompanied by a rearrangement of the molecule. Reaction 4 introduces collision products;

collisions between molecules and ions can produce peaks with higher mass number than the

molecular ion peak. Ordinarily, the only important collisions of this type are those which transfer

a hydrogen atom to the ion. This results in an increase in the size of the M + 1 peak (the peak

which occurs one mass unit higher than the molecular ion peak). The significance of this peak

will be discussed in a following section. The products from each of these reactions are recorded

as they pass into the detector. The mass spectrum, then, is a record of the masses of the positively

charged fragments (including the molecular ion) versus their relative concentrations. The peak

with the highest intensity in the mass spectrum is referred to as the base peak.

Thus a number of different reactions occur in the ionization region of the mass
spectrometer. Consider the molecule CH4 in detail. In one form of ionization, one of the valence

electrons of the molecule is "knocked out" and a cationic species, CH4A+ is left behind.

CH4 + 1e- 6 [CH4]A+ + 2e-

This reaction represents the loss of one of the 8 valence electrons which bond the 4 H's to the C

atom in CH4. The result is [CH4]A+ , which indicates that 7 valence electrons now bond the four

H's to the C atom resulting in a species which is positively charged. The • indicates the presence

of an odd number of electrons. In the above reaction, the CH4 molecule has lost 1 electron to

form the parent molecular ion. This parent molecular ion, being of high energy, then fragments

producing a new cation having a smaller M / Z and this gives rise to another

peak in the mass spectrum for the .CH3+ fragment.

[CH4]•+ + 1e- 6 CH3+ + 2e- + H+ Fragmentation

The fragmentation process will continue until no smaller fragments can be

formed. As indicated previously, this fragmentation may be also accompanied by a rearrangement

to form a more stable ion.

In interpreting a mass spectrum, the peaks recorded must be assigned to certain species which

would be produced during ionization, fragmentation or rearrangement. The approach to the

analysis thus depends on whether the spectrum was run for the purpose of the confirmation of a

chemical species, or it's identification. If one suspects the identity of the sample, one would look

for the molecular ion peak to see that it indicated the correct molecular weight, and then examine

the other peaks to see that they corresponded to the fragmentation pattern of the suspected species.

If the sample was run in an attempt to identify a species, one must identify the molecular ion and

then piece together the structure of the species from the observed fragment peaks. When a

spectrum is run for this purpose, one generally has ideas as to what the unknown species could be,

based on the components of the reaction. For samples with large molecular weights and

complicated formulae, a table such as J.H. Beynon's Mass and Abundance Tables for Use in

Mass Spectrometry may aid in identification. After identifying the molecular ion peak in a
spectrum of an unknown sample, the table may be consulted to find a list of possible formulae

with the appropriate molecular weight. There are also books containing spectra of known

compounds which may be referred to for proof of identification.

One way to study a spectrum is to examine a bar graph of peak height versus mass number, in

which the peak heights are expressed as a percentage of the base peak (i.e. the base peak is

assigned a height of 100%). The data are much easier to understand in this form. Another

common way of expressing data is in a table. The computer attached to the mass spectrometer

provides the data in both forms.

In 80 to 90 percent of organic compounds, the molecular ion peak is easily recognizable.

Here are some simple rules to help identify this peak:

1. The molecular ion peak must have the highest mass of any peak in the spectrum.

Actually, there may be one or two smaller peaks occurring one or two mass units higher than the

molecular ion peak. These are isotope peaks. The intensities of the isotope peaks relative to the

molecular ion peak can help identify the compound. Any peaks due to the presence of isotopes

will be smaller than the molecular ion peak; thus, the latter can still be identified. Table 1

indicates the natural abundances of the stable isotopes for the elements with which we will be

dealing. N.B. For compounds containing halogens, sometimes the peak of highest mass is

not the molecular ion

peak but rather is that of a fragment of the molecule from which a halogen atom has

already been cleaved.

2. The mass of the molecular ion must be even unless the molecule contains an odd

number of nitrogen atoms. This is known as the "nitrogen rule": a molecule of even-numbered

molecular mass must contain no nitrogen or an even number of nitrogen atoms; an odd-numbered

molecular mass requires an odd number of nitrogen atoms. For example, suppose we have a

sample of molecular mass 150. As previously mentioned there are a number of tables which list
the formulae of molecules at given molecular masses. Consulting one such table gives us a

variety of formulae with a molecular mass of 150: C8H10N4, C8H8NO2, C8H10N2O, C8H12N3,

C9H10O2, C9H12NO, and C9H14N2. On the basis of the nitrogen rule, three of these (C8H8NO2,

C8H12N3, and C9H12NO) can be ruled out as possibilities because they contain an odd number of

nitrogen atoms.

Table 1. Natural abundances of stable isotopes

% Natural Abundance
1
H 99.985
2
H 0.015
12
C 98.892
13
C 1.108
14
N 99.635
15
N 0.365
16
O 99.759
17
O 0.037
18
O 0.204
32
S 95.0
33
S 0.76
34
S 4.22 7 possibly visible in mass spectra at
low resolution
35
C1 75.53
37
C1 24.47 7 observable in low resolution mass
spectra
79
Br 50.52
81
Br 49.48 7 observable in low resolution mass
spectra
3. The peak at next lower mass must not correspond to the loss of an impossible or

improbable combination of atoms. Rarely do organic molecules lose more than four hydrogen

atoms, to give M-4 fragments (peaks occurring four mass units less than the molecular weight).

The next likely fragments are losses of a methyl group (M-15), NH2 or O (M-16), OH or NH3 (M-

17), H2O (M-18), F (M-19), HF (M-20), and C2H2 (M-26). Thus, if a molecular ion appears to

have lost 4 to 14, or 21 to 26 mass units, either the assignment of the molecular ion peak is wrong,

or the sample is a mixture of two or more compounds.

4. The most common fragments correspond to the most stable carbocations. Thus it helps to

know what factors help stabilize an organic cation. These factors follow very simple rules:

a). The more substituted the cationic center, the more stable the cation, eg what one means

by this is that non-hydrogen substituents (all of which contain more electrons than H) stabilize an

adjacent cationic center. Thus one expects branched hydrocarbons to fragment next to the branch

point.

b). Substituents with pi bonds or non-bonded electron pairs can stabilize a cationic center

through resonance. Examples include

You should take some time to review resonance structures and draw all the resonance structures of

these four species. Ions similar to 1 are formed during fragmentation of ketones, aldehydes, and

esters. Alcohols and ethers give ions related to 2. Amines give ions related to 3, and aromatic

molecules with an alkyl substituent give ions related to 4.

 Procedure for Identification of an Unknown

To illustrate how one would go about identifying an unknown sample, two examples follow.

Essentially, identifying an unknown sample by means of mass spectrometry entails detective work,

deducing the presence of certain atoms in the mystery compound. To make this task somewhat easier,

it is helpful to keep in mind some simple guidelines.

First of all, we will be working with a simple organic compound. Hence, the sample is most

probably composed of the following elements: carbon, hydrogen, oxygen, nitrogen, fluorine, sulphur,

chlorine or bromine. Whether or not the last three are present can be determined by the isotope peaks.

Chlorine, bromine, and sulphur, have stable, abundant isotopes which are about two mass units

heavier than the molecular mass of the more abundant isotope. As a result, any compound containing

one or more of these elements will have a noticeable peak occurring two mass units higher than the

molecular ion peak (this is the peak referred to as the M+2 peak). Clearly, if the M+2 peak is not

visible, then the aforementioned elements are not present in the sample.

To determine the presence of the remaining elements (carbon, hydrogen, nitrogen, oxygen,

fluorine), we need to examine the fragments. Tables 2 and 3 will be useful for this purpose.

Table 2 lists the atomic weights of certain elements, rounded up to the nearest whole number.

These are the weights used to calculate the formula mass of the unknown.
Table 2. Atomic weights for elements commonly found in organic compounds

Element Atomic Mass

Carbon 12
Hydrogen 1
Nitrogen 14
Oxygen 16
Sulphur 32
Chlorine 35, 37
Bromine 79, 81
Fluorine 19

Table 3. Uncharged fragments and the mass numbers at which they occur

Fragment Mass Number

HA M-1
CH3A M-15
NH2A M-16
O M-16
NH3 M-17
OHA M-17
H2O M-18
FA M-19
HF M-20
C2H2 M-26
CO M-28
CH3CH2 A M-29
CH3OA M-31
C3H7A M-43
CO2 M-44

Table 3 lists uncharged fragments which are commonly split off from a molecular ion. When
these species are lost from the molecular ion, they generate a peak at a mass number of [M-(fragment

mass)]. This information will be a great help in identifying the fragment peaks in a spectrum.

The following examples illustrate how to identify an unknown sample.

Example 1.

Fig. 2. Mass spectrum of an of unknown sample

1. One should first measure the peak heights with a ruler and calculate the height of each peak

as a percentage of the base peak (tallest peak in spectrum).

2. The next step in the analysis should be the identification of the molecular ion peak. The peak

having the largest mass number in the spectrum is found at 45 amu. Since it is of significant

intensity, it cannot be an isotope peak and it is unlikely that it is a peak due to the

rearrangement of ions. This peak also fulfills the third rule mentioned for identifying the

molecular ion peak since the peak at M-1 could correspond to the loss of a H atom. The
 absence of an M+2 peak indicates that there is no Cl, Br, or S in the sample.

Having determined that the mass of the molecular ion is 45 amu, one recalls the

"nitrogen rule". There must therefore be an odd number of N atoms in the molecule.

Furthermore, there must be only one N atom since the next lowest odd number of N's would

be three. The mass of these three N atoms alone would be 42, meaning that the remaining

3 units to make a total of 45 would have to be H atoms and there is no compound known of

empirical formula H3N3.

3. Since we are dealing with an organic species, the molecule must therefore be some

arrangement of C, H, N and possibly O atoms.

4. It is now useful to tabulate the peaks which are present in the spectrum as is done in Column

1 of Table 4. Column 2 indicates the relation of each peak to the molecular ion peak.

5. The next step in the analysis is to consider possible fragment assignments to peaks of low

amu as is indicated in Column 3. Also listed are possible assignments for the base peak since

it is of the greatest abundance.

6. Column 4 suggests what fragments could have been lost from the molecule upon referring

to Column 2. Possibilities are also listed in the case of the base peak.

7. Sometimes trace impurities are present in the spectrometer and these most frequently appear

as H2O (18 amu) and CO2 (44 amu). Upon examination of the data taken from the mass

spectrum in Example 1, peaks are found at 18 amu and at 44 amu. These peaks could

therefore be due to impurities and may not be related to the unknown sample. These

possibilities should be kept in mind and so are recorded in Column 5. Remember that the

presence of an impurity of this sort could also be increasing the intensity of a peak due to an

unknown fragment at that particular atomic mass. If a peak at, for example, x amu in the

spectrum is due solely to an impurity, there will be no corresponding peak at the M-x unless

there is a fragment of atomic mass x.

8. Now one is able to suggest possible empirical formulae. Remember, it has been determined
 that there is definitely one N atom in the compound. The only possible combinations of C,

N, H and O atoms with an atomic mass of 45 are a) C2H7N or b) CH3NO.

Table 4. Tabulated data from mass spectrum of Example 1 unknown.

Column 1 Column 2 Column 3 Column 4 Column 5

amu of Relation Possible Possible Possible
peak to M fragment fragment impurities
assignments loss from M

45 M molecular ion
44 M-1 loss of 1H CO2
43 M-2 loss of 2H
42 M-3 loss of 3H
40 M-5
32 M-13
31 M-14
29 M-16
28 M-17 base peak CO,C2H4,CH2N OH, NH3
27 M-18
26 M-19
18 M-27 H2O, NH4 H2O
17 M-28 OH, NH3
16 M-29 CH4, NH2, O
14 M-31 CH2, N

9. The next step is to postulate possible structures for these two empirical formulae.

Of the postulated structures, b) (iv) is very unlikely based on a knowledge of organic

chemistry. The molecule is much too strained to exist, and this possibility can therefore be
 eliminated. Even without a knowledge of any organic chemistry, one would expect to see

in the mass spectrum of b) (iv), peaks due to the fragments NH (15 amu) and CH2O (30

amu). These peaks are absent in the spectrum provided of the unknown.

10. We now predict how each of these structures would fragment.

a)(i) should show an intense peak at 30 amu (CH2—NH2). This is not observed.

a)(ii) should show peaks at 15 amu (CH3) or M-15 (CH3NH), and a very

strong peak at M-1 (CH2—NH—CH3).

b)(i) should show a peak at 29 amu (H—C=O) and at 28 (CO). These are seen

along with other peaks.

b)(ii) should show a peak at 15 amu (CH3), and at M-15 (N=O). These are not

found.

b)(iii) should show a peak at M-17 (due to loss of OH), and at 15 amu (N—H).

By the process of elimination, the structure of the unknown has thus been identified as:

11. On further examination of the fragmentation pathway for HCONH2, one finds that there are

peaks seen for all major fragments; CO, H, NH2, and HCO.
 Example 2

Fig. 3. Mass spectrum of the second unknown sample

1. In the graph in Figure 3 we see a small peak at 85 amu, a large peak at 86 amu, and a small peak

at 87 amu. The peak in the spectrum having significant intensity and fulfilling the other

necessary requirements of a molecular ion peak, is the peak at 86 amu and so is identified as

such. The spectrum shows the absence of C1, Br, and S in the sample. An M+1 peak is

observed at 87 amu. Since the molecular ion peak indicates an even molecular weight, there

cannot be an odd number of N atoms in the compound.

2. We have now determined that the compound must be comprised of some combination of C and

H, and possibly O, and/or an even number of N.

3. The other prominent peaks in the spectrum appear at the following atomic masses: 71, 57 (base

peak), 56, 55, 43, 42, 41, 39, 29, 28 and 27 amu.
4. Assignments for the peaks of low and characteristic atomic mass are now postulated. Since the

base peak is at a rather high atomic mass, there could be a number of possibilities for it's

assignment.

Base peak: 57 amu C4H9, C2H5C=O

29 amu C2H5, CNH3

28 amu CO, CNH2, C2H4, N2

27 amu C2H3, CNH

5. Possibilities for assignments of peaks are now considered based on the possible fragments that

could have been lost from the molecular ion.

85 amu M-1 loss of 1H

71 amu M-15 loss of CH3

Base peak: 57 amu M-29 loss of C2H5, CH3N, HC=O

NB: No peaks appear at M-16 or M-17 which would suggest the loss of NH2 or NH3

fragments, so it seems very likely that there is no N in the sample. The absence of these

peaks may also suggest that there is no oxygen either.

6. The peak observed at 44 amu could be due in whole or in part to the presence of a CO2 impurity.

7. Enough information has been collected to suggest possible empirical formulae. So far it has

been determined that there is a CH3 group present (M-15). The molecule may be a simple

hydrocarbon [C6H14], or it may be an aldehyde or ketone [C5H10O] (or even possibly an

unsaturated ether or alcohol).

i) If the molecule contains oxygen, the base peak at 57 amu must be due to C3H5O, ie

which would be formed from fragmentation of

Both of these molecules could lead to the (M-15) and to the 57 amu peaks, but it would be very

difficult to explain the relatively intense peaks at 27-29 amu and 38-44 amu. If the C3H5O peaks are

so stable, all other peaks in the spectrum should be much weaker in intensity by comparison. Thus

we eliminate oxygen-containing molecules from further consideration.

ii) It would seem very likely that the unknown molecule is a simple hydrocarbon with the

empirical formula C6H14.

8. There are several possible structures for this empirical formula:

9. All these structures would give rise to the same major spectral peaks as observed in the unknown

spectrum provided. The difference in the spectra would be the relative abundance of each peak.

Notice that for the branched isomers, we should be able to predict the major fragmentation

pathways. Branched isomers prefer to fragment at the branch point. For (ii) we expect the two

3E ions at (M-15) and (M-29) to be the strongest in the spectrum.. This explains the peak at 57

amu but not the tiny peak at (M-15). For (iii) we expect a very large peak at 57 amu (M-29) but

only weak peaks in the region of 27-29 amu and 39-44 amu. (iv) should give major peaks at (M-
 15) and at 43 amu (C3H7(+)) but not at 57 amu. (v) should fragment predominantly between the

two 2E carbons to give a major peak at 43 amu. If a case such as this arose in a laboratory

situation, the experimenter might check mass spectra reference books to make a comparison of

the known spectra to his/her experimental spectra.

10. The following is reference spectral data for n-hexane, structure (i).

Fig. 4 Spectral data for the pure n-hexane

We can see that the unknown spectral data matches almost exactly the reference data. This then

confirms that the unknown compound is n-hexane. The several small additional peaks in the

unknown spectrum can be attributed to impurities.

Having now worked through two examples of how to approach the identification of an unknown

sample by means of it's mass spectrum, let us now summarize the steps one should follow:

1. Identify the molecular ion

Remember the following.

 a. It must be the peak of largest mass of significant intensity.

b. The peak of next lowest mass must not correspond to the loss of an impossible or

improbable combination of atoms.

Note the following.

a. Is there an M + 2 isotope peak indicating the presence of C1, Br, or S?

b. Is there an M + 1 peak which could be due to a rearrangement?

c. Consider the "nitrogen rule".

2. Having considered all the points mentioned in step 1, try to decide which atoms comprise the

molecule if it is a simple organic species. The possibilities are: C, H, O, N, S, F, C1 and Br.

3. Study or tabulate peak information.

4. Consider possible fragment assignments to peaks of low atomic mass. Also consider the

base peak if it is reasonable to do so based on it's mass.

5. Consider what possible fragments could have been lost for peaks close to the molecular ion

peak. Also consider possible fragments lost from the base peak if possible.

6. Look for trace impurities such as H2O or CO2 at peaks 18 amu and 44 amu respectively.

7. Start counting atoms to suggest possible empirical formulae.

8. Postulate structures for empirical formulae based on a knowledge of basic structure, bearing

in mind any information gathered to this point.

9. Consider fragmentation pathways for the postulated structures to determine the agreement

with the actual spectrum. Identify the unknown structure if possible.

10. Check that all the major peaks one would expect to see for the determined structure are

indeed present in the spectrum. If it is necessary, consult mass spectral reference books to

confirm the identity of the unknown.

11. Account for the relative peak heights through calculations that use the relative isotope

abundances. Remember that a given peak may be due to more than one ionic species.
Applications

Mass spectrometry has a number of applications to contemporary science, in the fields of

chemistry, physics, geology, ecology, biology (medicine), and astronomy. In the field of chemistry,

mass spectrometry has been used in the determination of molecular masses and molecular formulae,

as well as in the measurement of dissociation energies and bond lengths. In physics, it is used in the

studies of nuclear reactions, nuclear shell structure, isotope abundances, properties of thin films, and

in the measurement of trace quantities of uranium and lead in minerals and meteorites. In geology,

the isotope abundance data is applied to the dating of rocks and minerals by isotopic ratio

measurements. Here, the mass spectrometer is useful since it permits the extension of the studies

to include non-radioactive species such as 13C, 17O, 18O, 15N, etc. In ecology, the mass spectrometer

is used to monitor pollution in the air and water, since its sensitivity is such that it can detect trace

elements. In the field of medicine and forensic science, mass spectrometry is used in the analysis

of blood, the monitoring of bone growth, and in the area of toxicology, (again the sensitivity of the

instrument allows it to detect trace amounts of toxic substances). In astronomy, the mass

spectrometer is used in the analysis of dust particles, soil samples from other planets and the

composition of the atmosphere of other planets. It is used in the analysis of meteorites, giving

important data as to the age of the meteorites, and clues as to the nuclear reactions associated with

the formation of the solar system. Finally, mass spectrometry is used in the attempt to detect "life"

on other planets; soil samples are searched for organic compounds of biological interest, which can

be distinguished from organic compounds which are not of biotic origin.

Pre-lab Questions

Answer the questions that are on pages 51 - 52.

Procedure

Work to be completed within your scheduled lab period:

During the lab period in which you are scheduled to do this experiment, you will be shown a film

on mass spectrometry. Then you will be given the mass spectrum of one or more unknown organic

compounds whose identity you are to determine.

It is of utmost importance that prior to entering the lab you be familiar enough with the

approach to the analysis of a spectrum outlined in the preliminary discussion that you can proceed

with the identification of your unknown. The remainder of the lab period will thus be spent on the

determination of the identity of your sample under the guidance of your demonstrator.

Before leaving the lab you will be required to submit a data sheet indicating various information

which you should have deduced from the spectrum of your unknown during the lab period.

Your report should include an account of your deduction of the identity of your unknown

showing how both the positions and the relative abundances of the peaks were used in the

identification.

References

These references are on reserve in the UTM library.

QC 454 M27 McLafferty, F.W.: Interpretation of Mass Spectra, 2nd and 3rd editions.
QC 454 S515 Shrader, S.R.: Introductory Mass Spectrometry.
QD 95 B48 Biemann, K.: Mass Spectrometry: Organic Chemical Applications.
QD 95 H55 Hill, H.C.: Introduction to Mass Spectrometry, 2nd edition.
QD 271 W543 Williams, D.H.: Principles of Organic Mass Spectrometry.
Name:__________________________ Student Number:_____________________

Lab Section No.:_________________

Pre-Lab Questions

1. Bromine has two naturally occurring isotopes, 79Br , abundance 50.52%, and 81Br, abundance

49.48%. The most stable form of bromine under standard conditions is as the diatomic

molecule, Br2 . In a mass spectrum of bromine, at what m/z values would you expect to see

peaks and what would you expect the relative height of the peaks to be? What species would

account for each peak? Explain.

 Data Sheet

Name:_______________________________ Student No.:___________________

Lab Section No.:______________________ Date:_________________________

Unknown No._________________________

This should be a record of the deductions that you have made during your lab period and your

preliminary identification of your unknown.

 EXPERIMENT 2

Qualitative Analysis of Cations

Introduction
There are two kinds of analysis that are essential to experimental chemistry. The
identification of a compound, or the components of a mixture, is known as qualitative analysis.
The accurate determination of the amounts of substances in a mixture, or the determination of the
relative masses of the elements in a compound, is called quantitative analysis. One of the
challenges of modern chemistry is to design improved methods for analyzing a great variety of
different kinds of materials, some of them often present in a complicated mixture only in trace
amounts.
In this experiment, you will carry out some of the standard tests for the qualitative
detection of some common cations in aqueous solution. These are some of the most interesting
and colourful reactions. A full understanding of the methods depends ultimately on
understanding the principles of chemical equilibria as applied to precipitation, acid-base, and
oxidation-reduction reactions, subjects that we will investigate throughout this course.
In this experiment, you will be given a known solutions of lead nitrare, copper nitrate,
aluminum nitrate and lead nitrate and an unknown solution containing some of these ions. The
purpose of the experiment is to familiarize yourself with the characteristic reactions of each of
these ions and, by comparing the results of the same tests performed on the unknown solution,
to discover which ions are present in your particular unknown. .

One problem in the experimental work is in adopting a cookbook approach - a slavish

concern with measuring and mixing reagents, a line by line following the directions. There is a
danger that the chemistry, the raison d’etre of the scheme, is likely to be neglected in the rush to
complete the experiment. Avoid this pitfall by thinking out each experimental step and writing
out the relevant equations before proceeding to the next step. You will find that there is a great
deal to be learned.

Experimental Hints
1. Cleanliness is essential. Take care not to contaminate any reagent bottles.
2. For reactions which need to be carried out at elevated temperatures, a hot water bath
should be used. This consists of a beaker of water heated to 80-90EC on a hotplate and
into which your test tubes can be placed (not immersed!).
3. In separating a precipitate from a solution by centrifugation, seal the test tube with
parafilm and be sure that the centrifuge is properly balanced. When separation is
complete, the liquid may be removed using a Pasteur pipette.
4. Whenever reagents are combined, be sure that the resulting solution is thoroughly mixed.
Diffusion in solution can be a very slow process and many tests will appear not to work if
mixing is incomplete. Either seal the tube with parafilm and shake vigorously or stir with
a glass rod.
5. H2O means distilled H2O in all cases.

Recording Observations
You will learn most in this experiments if you make careful observations and describe
exactly what happens. The procedure and observations made at each stage of the reactions of the
known ions and the deparation of the ions in the unknown solutionand the tests for each metal
ion, should be entered in your notebook as soon as they are made, together with your conclusion
about whether the test for a particular ion in your unknown solution was positive or negative.
This is done most conveniently in tabular form, for example:
 Observations Conclusions Unknown
Test unknown
1. 2.5 mL of unknown white ppt. Pb+2 present
#
0.2 mL of 6 M HCl
stir well, centrifuge.
add 1 drop of 6 M HCl
to
decantate

2. ppt. from 1 yellow ppt.

add 2.5 mL H2O
heat
add 3 drops
1M K2CrO4

Observations should be those actually made in the laboratory, not those that you expect to
make, i.e. no observation entries should be made in this table before the experiment is
performed.

References
Good discussions of the experimental procedures designed to analyze complicated
mixtures are to be found in most textbooks on qualitative analysis. You will find it useful to
refer to one of these (listed at the end of the experiment), and to your textbook, in understanding
reactions and writing equations.
 In this experiment, you will be given solutions of the nitrates of lead(II), aluminum(III),
Cu(II) and iron(III). You will also be given an unknown solution containing one or more of
these nitrates. The objective of the experiment is
1. to separate the cations of the unknown mixture contanining one or more of the nitrates
of lead, aluminum, copper and iron, it is precipitated successively as suitable
insoluble salts and then to use selected specific reactions with them to confirm the
2. analyses.

The experimental methods used are illustrative of the kind of qualitative analysis scheme
that can be used to detect and separate quite complex mixtures containing metal ions.

Pre-lab Questions
Answer the four pre-lab questions on pages 26 - 28.

Procedure
Separation and Identification of Pb2+(aq), Fe3+(aq), Al3+(aq) , and Cu2+
Volumes are approximate. All work excepting the centrifugation should be done in
the fume hood.

1. To about 2. mL of your sample in a test tube, add 5 drops (~0.2 mL) of 6 M HCl(aq). Mix
well and centrifuge. Decant the clear liquid into a clean test tube and save it for Step
3(for the analysis of copper, aluminum and iron). Add 1 drop of HCl(aq) to it to make
sure the precipitation is complete. If a precipitate forms, mix well and centrifuge again.
Decant the clear liquid into a clean test tube and save it for Step 3.
2. The precipitate obtained by the addition of HCl to the test solution is PbCl2. To the
precipitate from Step 1, add 2.5 mL of distilled water and heat in a boiling water bath
for at least three minutes, stirring constantly. The precipitate should dissolve. To
confirm the presence of lead, add a few drops of 1 M K2CrO4(aq) to the clear liquid. The
formation of a yellow precipitate of PbCrO4(s) confirms the presence of lead.
3. Test the clear liquid from Step 1 with pH paper. It should have a pH of about 0.3. Add
0.5 mL of 1 M thioacetamide and mix well. Heat the test tube for at least 5 minutes in a
boiling water bath. Cu2+ and any Pb2+ remaining from Step 1 will precipitate as CuS and
 PbS. Continue to heat the test tube for another 2 minutes to complete the precipitation.
Centrifuge and decant the clear solution into a clean test tube. Save it for Step 7(for
the analysis of aluminum and iron).

4. To the precipitate from Step 3, add 0.5 mL of water and 0.5 mL of 6M HNO3 . Heat
the test tube in a boiling water bath until the reaction is complete. The resulting solution
will contain Cu2+ and any Pb2+ that was not completely precipitated in Step 1.

5. Cool the solution from Step 4 and then add 6 M NH3, mixing well, until the solution is
basic to litmus paper. Add an additional few drops of the 6M NH3. If the resulting
solution is deep blue, it indicates the presence of the Cu(NH3)42+ complex ion.
6. To confirm the presence of copper, add 6 M acetic acid to the blue solution from Step 5
, mixing well, until the colour fades and the solution is acidic to litmus. Then add a drop
or two of 0.1 M K4Fe(CN)6 which forms a red-brown precipitate of Cu2Fe(CN)6 if copper
is present.
7. To the clear solution from Step 3, add 0.2mL of 6 M HCl, mix well and centrifuge.
Discard the precipitate. To the clear solution, add 0.5 mL of 3% H2O2 (hydrogen
peroxide) and then, drop by drop, 6 M NaOH(aq), mixing well, until the solution is basic.
Then add a few drops more. Mix for a minute, boil for 2 to 3 minutes and then
centrifuge. Decant the clear solution into a test tube and save for Step 9(for the analysis
of Al). The precipitate is Fe(OH)3. How do you know that it cannot be Fe(OH)2?.
8. To confirm the presence of iron, add 0.5 mL of water and 0.5 mL of 6 M H2SO4(aq) to the
precipitate from Step 7. Stir for a minute or two and centrifuge the solution if it is not
clear. Take half of the clear solution, add 1 or 2 drops of 0.1 M KSCN(aq) (potassium
thiocyanate). Formation of a deep red solution of the FeSCN2+(aq) complex ion confirms
the presence of iron.
9. To the clear filtrate from Step 7 add 6 M HNO3(aq) slowly, and mixing well, until the
solution is acidic. If necessary, reduce the volume to 1.5 to 2 mL by boiling it down..
Add 6 M NH3(aq) drop by drop until the solution is basic to litmus. Stir for a minute or
two. A light, gelatinous precipitate of Al(OH)3 indicates the presence of aluminum.
10.. To confirm the presence of aluminum, centrifuge the product of Step 9 and then
dissolve the precipitate in 0.5 mL of 6 M HNO3(aq). Add 0.5 mL of water and 1 drop of
aluminon reagent and stir. At this point the solution is pink. Add 6 M NH3(aq) drop by
 drop, stirring well, until the solution becomes basic to litmus. Al(OH)3(s) should reform
and adsorb the red colour from the test reagent, leaving the solution essentially colourless.
Centrifuge and check the colour of the solution.
11. At the end of the lab, test tubes should be rinsed with water, the rinse being put in the
chemical waste bottles in the common fumehood. Used test tubes and Pasteur pipettes
should be put in the green pails in the common fume hood and rubber bulbs should be
returned to the common bench.

References (refer to newer editions where available)

1. Lagowski and Sorum, Introduction to Semimicro Qualitative Analysis, 8th edition, Prentice-Hall
(2005).
2. Charlot, Qualitative Inorganic Analysis, John Wiley Sons, Inc (2007).
3. Slowinski, Qualitative Analysis and the Properties of Ions in Aqueous Solution, Saunders (1971).
4. Vogel, A Textbook of Marcro and Semimicro Qualitative Inorganic Analysis, Longman (1962).
Name:________________________ Student No:___________________
Lab Section No.________________

Pre-lab Questions

1. Write balanced equations for the reactions of solutions containing a) Pb2+(aq), b) Fe3+(aq),
Al3+(aq), and d) Cu2+(aq) in reactions in the analyses step 1 to step 10. Include all reactions that are
used to separate the cations as well as the confirmatory tests.

________________________________________________________________________
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_
2. Complete the Flow Chart, showing the complete analytical scheme and all of the
confirmatory tests for the ions.

Flow Chart for the Separation Scheme for Pb2+, Fe3+, Al3+ , and Cu2+

Mixture of Pb2+, Fe3+, Al3+ and Cu2+

* HCl(aq)
+))))))))))))))))))))))))))))))))))))))),
white precipitate filtrate
PbCl2(s) Fe3+, Al3+, Cu2+ and some Pb2+

* thioacetamide
. +))))))))))))),
precipitate filtrate
CuS and PbS Fe and Al3+
3+

* *
3. After reference to the Flow Chart, write equations for each of the reactions involved in
the separation of Pb2+(aq), Fe3+(aq) , Al3+(aq) and Cu2+ . Note the colours of any
precipitates formed and the colours of any solutions.
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________________________________________________________________________
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________________________________________________________________________

4. Write balanced equations illustrating the reactions of each of the metals (not metal ions)
Pb, Fe, Al and Cu with a) hydrochloric acid and b) nitric acid.
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________

_______________________________________________________________________

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 DATA SHEET
Name:__________________________ Student
No.:____________________
Lab Section No.:_________________ Date:_________________________
_
Unknown Solution Number: ________
Cations Present:________________________________________

Observations Conclusions Unknown

Test Known Unknown
 Experiment 3

THE HEAT OF IONIZATION OF A WEAK ACID

Introduction

Thermodynamics is the study of energy changes in a system, 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 mechanical 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

ÄE = Efinal - Einitial (1)

According to the first law of thermodynamics

ÄE = 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

environment. If the volume decrease is ÄV, and the constant pressure exerted on the system by the

surroundings is P, the work done on the system is !PÄV, resulting in an energy content increase in the

system by this amount. At constant pressure we can write

ÄE = q + w = qp - PÄV (3)
 or qp = ÄE + PÄV (3')

qp, the change in heat content of the system at constant pressure, is defined as its change in enthalpy,

ÄH. Thus, we can write

ÄH = Hfinal - Hinitial = qp = ÄE + PÄV (4)

In a liquid system, the change in volume occurring under normal conditions at constant pressure is

small, so that PÄV work is negligible; in this case ÄH = ÄE = qp, and ÄH 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 ionization of a salt or an acid or base.

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

insulator, which makes a suitable calorimeter (Figure 1.). The temperature change from a reaction

carried out inside the calorimeter can be measured, then the change in heat content may be calculated

if the total heat capacity of the system (calorimeter and contents) is known. If ÄT is the temperature

change and Cp is the total heat capacity of the system at constant pressure

qp = CpÄT (5)

where

ÄT = Tfinal - Tinitial.
 The heat capacity of the calorimeter includes those of all of its parts (e.g. the styrofoam cup

and thermometer) and must be determined experimentally. One way of doing this would be to supply

heat to the calorimeter containing a known amount of water by means of a resistance heater.

Another way, and the one we use in this experiment, 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 cold water* + * heat absorbed by calorimeter*

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

q = Vh ñ CpH2O ÄT = (heat lost by hot water) (7)

where Vh is its volume in mL, ñ is its density in g mL-1, CpH2O is its specific heat capacity in

J g-1 K-1, and ÄT 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 ÄTN, 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 ÄTN, and the heat absorbed by the cold water and the calorimeter can

be expressed as

q = Vc ñ CpH2O ÄTN + Cpcal ÄTN

= (heat absorbed by cold water) + (heat absorbed by calorimeter) (8)

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

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 neutralization.

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 (ÄT = ÄT'). 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 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
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 ÄT = T2 -

T1, where T2 is the high temperature extrapolated back to the staring time, and T1 is the initial

temperature.
Pre-lab Questions

Answer the pre-lab questions on page 83.

Procedure

1. Heat Capacity of Calorimeter

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

Transfer it to the clean dry calorimeter, which is mounted on a stirring plate and fitted

with a digital thermometer calibrated to ±0.1EC. Put a magnetic stirring bar into the

calorimeter and make sure it does not hit the tip of the thermometer while stirring.

Record the temperature when the thermometer reading remains constant.

b. Take 50 mL of warm tap water (~40EC). Quickly measure the exact temperature and

immediately transfer it to the calorimeter, as quickly and completely as possible. With

a stopwatch, 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. The magnetic

stirring should be on throughout this process.

c. 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?

d. 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.

2. Heats of Neutralization

In this experiment, the heats of neutralization of the strong acid, hydrochloric acid, and that

of a weak acid will be determined.

 The strong base is sodium hydroxide of a concentration given on the stock bottle in the

lab.

a. 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.

b. Meanwhile, rinse out the graduated cylinder with tap water, distilled water and a few

mL of the stock HC1(aq). Measure out 50 mL of the 1.0 M HC1(aq). Allow to stand

until its temperature is constant and equal to room temperature. Record this

temperature.

c. 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.

d. 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 ÄT and ÄTN for the acid and base, respectively.

e. 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.

f. Repeat steps a. to e. using the weak acid solution instead of the HCl solution.
You will not see this part of the experiment in the lab video. However,you
will get the data for this part to write the report.

Calculations
1. Using data from each of the runs, calculate the heat qp evolved in each neutralization. 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. Calculate the number of

moles of acid and base neutralized in each case.

2. Enthalpy of Neutralization of the Strong Acid-Strong Base

Since both acid and base are fully ionized, the neutralization may be expressed as

H3O+(aq) + OH-(aq) 6 2H2O(l)

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? Suppose that you repeated the experiment using 1 M HNO3(aq). Would you expect

to obtain the same value?

3. Weak acid neutralization

Since a weak acid is partially dissociated into ions in aqueous solution,

HA + H2O º H3O+ + AG,

its neutralization may be considered to occur in two steps:

a. the neutralization of the H3O+ initially present via the reaction

H3O+ + OHG º 2H2O,

whose ÄH was calculated in Part 2, and

b. the neutralization of the undissociated weak acid via the reaction

HA + OHG + H2O º AG + 2H2O,

whose ÄH is to be calculated now.

 Heat released by reaction a. = ÄH kJ mol-1 from Part 2. x mol H3O+ neutralized.

In the calculations, use the KA value that you determined in Experiment 7. Note that in

calculating the [H3O+] , the semi-exact-weak acid approximation is valid for acetic acid, but

it may not be valid for all organic acids. In those cases, only the semi-exact approximation

can be made and the quadratic equation must be solved in order to find [H3O+].

4. ÄH of ionization

Using your experimental values for ÄH1 and ÄH2, calculate the enthalpy of ionization

of the weak acid, ÄH3.

H3O+ + OH- º 2H2O ÄH1

HA + OH- + H2O º A- + 2H2O ÄH2

HA + H2O º H3O+ + A- ÄH3

5. Entropy of ionization

a. Using the value of KA determined in Experiment 7, calculate the standard free energy

change for the reaction of the weak acid with water.

 ÄGE = -RT 1n KA

b. Using the ÄHE of ionization determined in this experiment and the ÄGE calculated

above, determine the ÄSE of ionization.

ÄGE = ÄHE - TÄSE

Name: Student No.:

Lab Section No.:

Pre-lab Questions

1. 50 mL of water at 51.9EC were mixed with 50 mL of water at 23.2EC in a calorimeter also at

23.2EC. The final temperature was 33.1EC. 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)

2. When 5.00 g of NaOH(s) are added to 100 g of water (using the same calorimeter as in
Question 1), the temperature rises from 25.0 to 37.5EC. Calculate the molar heat of solution,
i.e. ÄH for the process
NaOH(s) 6 Na+(aq) + OH-(aq)

Assume that the specific heat of water is 4.18 J g-1 K-1 and that of the NaOH(aq) solution is
the same.
 Data Sheet

Name: Student No.:

Lab Section No.: Date:

1. Heat Capacity of the Calorimeter

volume (mL) initial temperature (oC)

hot water

cold water

uncertainty in volumes =

uncertainty in temperatures =

temperature of mixture (oC) time after mixing (s)

 EXPERIMENT 4
Determination of a Molar Mass by Freezing Point Depression

Introduction
Determination of the molar mass is usually one of the first experiments attempted on
unknown compounds. There are a variety of ways to do this, but the technique used in this
experiment is based on a colligative property of solutions. A colligative property is one that
depends primarily on the number of molecules in a solution and not on the nature of the
molecules. These include vapour pressure lowering, boiling point elevation and freezing point
depression, the latter of which will be employed in this experiment.
When a non-volatile solute is dissolved in a solvent, the equilibrium vapour pressure of the
resultant solution is always less than the equilibrium vapour pressure of the pure solvent. This
lowering of the vapour pressure shows that there is a lesser tendency for the solvent molecules to
escape into the vapour phase in the presence of dissolved solute. One consequence of the lowering
of the vapour pressure is that the freezing point temperature of a solution (or mixture) is lower
than that of the pure solvent. This relationship is shown graphically in Figure 1 which shows the
vapour pressure as a function of temperature for each of the solid and liquid forms of the solvent
and for a solution of a non-volatile solute. Note that the vapour pressure curve for the solution
lies below that of the solvent. At the freezing point, the solid and liquid are in equilibrium. When
the solvent freezes, the solid that separates out is pure solvent. When the solution freezes, the
solid that separates out is also pure solvent. It can be seen from Fig. 1 that the temperature at
which the straight solvent line and the liquid solution curve meet is lower than the temperature at
which the straight solvent line meets the liquid solvent curve.
 Figure 1. Vapour Pressure Lowering and Freezing Point Depression

The amount by which the freezing point is lowered depends upon the concentration of the
solution, given in units of molality, and the molal freezing point depression constant, Kfp, which is
characteristic of the solvent. ÄTfp = m Kfp or, for solutes which dissociate in solution, ÄTfp =
i m Kfp where i is the number of particles generated in solution per molecule of solute (referred to
as the van’t Hoff factor). In this experiment the solute is molecular and i will equal one. The
concentration of the solution is determined in molality, m. The molal freezing point constant, Kfp,
is specific for each solvent. Some representative values are shown below.
Solvent Kfp (°C kg/ mol)
water 1.86
cyclohexane 20.00
camphor 5.95
stearic acid 4.50

In Steps 1 - 6 of the procedure of this experiment the freezing point of pure stearic acid will
be determined. In Steps 7 - 10, a weighed quantity of an unknown compound will be added to the

pure stearic acid and the freezing point of the mixture will be determined. The difference between

the freezing point of pure stearic acid and that of the mixture is the freezing point depression,

ÄTfp. Each freezing point will be determined by measuring temperature as a function of time as

the liquid is cooled to its freezing point and plotting cooling curves such as those seen in Figure

2. Knowing the molal freezing point constant for stearic acid, the molar mass of the unknown

sample can be determined by using ÄTfp = m Kfp.

Figure 2. Sample Cooling Curves for a Fatty Acid

Pre-lab Questions

Answer the pre-lab questions on pages 66 - 67.

Procedure:

1. Prepare a hot water bath by filling a 400 ml beaker ¾ full with distilled water and heating

with a hot plate to near boiling. Place 2-3 boiling chips in the beaker.

2. Prepare an insulating jacket for the reaction tube, tube A. Wrap a double layered strip of

paper towel around an 16 x 150 mm test tube, tube A, and fit it into a 20 x 150 mm test tube,

tube B. Carefully remove tube A, leaving the paper towel in place in tube B. Tube B and the

paper towel are the insulating jacket (see Figure 3). Tape the paper towel to the top of the

tube. The insulating jacket prevents premature cooling due to contact with the skin or

another surface and should not be removed from tube B during the experiment.

3. Determine the mass of tube A in a 100 mL beaker.

4. Weigh out about 6 grams of stearic acid into a large weighing boat and transfer it to tube A

using the plastic mini-funnel. Using the same balance, determine the exact amount of stearic

acid employed by reweighing the beaker with tube A and the stearic acid.

5. Suspend tube A containing the fatty acid sample in the hot water bath to melt the fatty acid.

After the fatty acid sample has completely melted, place the thermometer and the stirring ring

in the fatty acid sample and continue heating and stirring until the temperature rises to about

95 °C. From this point on and until the end of the experiment, the thermometer and

stirring ring are not to be removed from the fatty acid sample to prevent loss of material

and contamination of bench tops with fatty acid.

6. Note: This step is to be performed relatively quickly. Remove the test tube A containing the

fatty acid sample from the water and quickly dry the outside with paper towel. Place test

tube A into the previously prepared insulating jacket (test tube B). Quickly begin stirring

while watching the temperature until it reaches 85 °C (record this as the temperature at time
 = 0 s). Begin recording the temperature of the sample every 30 seconds for 6 minutes.

Hold the test tube in your hand and do not place the test tube on any surface to prevent

speedy heat transfer. Repeat steps 5 and 6 by remelting the same fatty acid sample. The

two sets of data collected will be used to determine the freezing point of the solvent,

7. To the stearic acid sample used above, add approximately 0.75 g of an unknown

compound. Exactly 0.75 g is not needed, but you must know exactly how much is added

to the nearest 0.1 mg.

8. Repeat steps 5 and 6 on the mixture from Step 7.

9. Add an additional 0.75 g of the unknown to the mixture from Step 7. Again, exactly 0.75 g

is not needed but you must know the exact mass added to the nearest 0.1 mg.

10. Repeat steps 5 and 6 on the mixture from Step 9.

Figure 3. Schematic diagram for the construction of an insulating jacket.

Calculations

1. To accurately determine the freezing points of pure stearic acid and each of the mixtures,

“cooling curves” of temperature (y-axis) versus time (x-axis) are plotted. Data where the

temperature changes by more than 0.5 °C per 30 seconds is plotted as one series and data where

the temperature changes by less than 0.5 °C per 30 seconds as a second series. A best fit line is

then calculated for each series and the freezing point is obtained by finding the point of

intersection of the two best fit lines, see Figure 2. From the cooling curves, determine the

freezing point of the pure stearic acid and of each of the mixtures.

2. Find the change in freezing points, ÄTfp, for the mixtures by comparing the freezing point of each

to the freezing point of pure stearic acid.

3. Use this to find the molality of each mixture using the equation ÄTfp = m Kfp
4. Use the molality to determine the moles of unidentified sample added in each trial. NOTE: For

the second addition of unidentified sample you are calculating based on the total number of

moles added (in Steps 7 + Step 9).

5. Determine the molar mass of your unknown.

6. Identify your unknown from the list below.

Myristic Acid

C14 H28 O2

Palmitic Acid

C16 H32 O2

Lauric Acid

C12 H24 O2

7. Experiments similar to this one are commonly done in many first-year chemistry courses. They

often use cyclohexane as the solvent and compounds such as p-dichlorobenzene, biphenyl, and

naphthalene as the unknown solutes. In the discussion of your report, describe the advantages

of this experiment over those.

Name:______________________________

Lab Section No.:_____________________ Student No.:____________________

Pre-lab Questions

1. Explain why the temperature gradually drops as a mixture is in the process of freezing.

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

______________________________________________________________________________

2. As a result of a manufacturing error, a thermometer was miscalibrated by +2<C . If this

thermometer was used in this experiment, would it cause the determined molar mass to be higher,

lower or the same as it would be had a properly calibrated thermometer been used? Explain.

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________
3. Why is molality, and not molarity, used to express concentration in the equations for freezing

point depression and boiling point elevation?

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

______________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

______________________________________________________________________________
 DATA SHEET

Name:______________________________ Student No.:____________________

Lab Section No.:_____________________ Date:_________________________

mass of beaker + tube A (Step 3):_________________________

mass of beaker + tube A + stearic acid (Step 4):______________

mass of stearic acid:_____________________________________

Cooling Curve Data for Pure Stearic Acid

Trial 1 Trial 2
Temp (NC) Time (s) Temp (NC) Time (s)
Cooling Curve Data for Mixtures

Unknown Solute No.:_______

Mass of unknown added in Step 9:_______

Mass of unknown added in Step 7:_______
Total mass of unknown in Step 9:________
Temp (<C) Time (s) Temp (<C) Time (s)
 Experiment 5

DETERMINATION OF THE KSP AND STANDARD

THERMODYNAMIC PARAMETERS FOR DISSOLVING Ca(OH)2
Introduction
Calcium hydroxide, Ca(OH)2, also called slaked lime, is commercially produced by reacting lime,
CaO, with water in a process called slaking. It is also sometimes called pickling lime because of its
use in food preserving. This is an interesting case in which a compound which under certain
conditions and at certain concentrations can be toxic is, at other concentrations non-toxic. “Ca(OH)2
is widely used in industry because it is inexpensive and abundant. For example, it is used in scrubbing
stack gases to remove sulfur dioxide from the exhaust of power plants and factories. It is also widely
used in water treatment plants for softening hard water, which involves the removal of ions such as
Ca2+ and Mg2+, ions that hamper the action of detergents.” 1
In this experiment the solubility
properties of Ca(OH)2 will be investigated.

Pre-lab Questions
Answer the pre-lab questions on page 91.

Procedure
Ca(OH)2 IS A STRONG BASE. CONTACT WITH SKIN MUST BE AVOIDED.
1. To prepare the saturated solution of Ca(OH)2 weigh about 3.6 g of Ca(OH)2 . In the fume
hood, transfer the contents of the vial into a 250 mL beaker. Add approximately 180 mL of
distilled water and stir at room temperature for about 15 minutes. Let the solution stand,
undisturbed, for a few minutes to allow most of the solid to settle at the bottom of the
beaker. Measure the temperature of the solution. Fit a clean, dry 250 mL Erlenmayer flask
with a long-stemmed funnel. Add a piece of fluted filter paper to the funnel. To filter the
Ca(OH)2 solution, carefully pour it down a stirring rod and into the funnel collecting the
clear solution in the flask. This is your saturated solution of Ca(OH)2 (A). Cover the flask
with a watch glass and leave it in the fume hood when not in use.

Use the same procedure to prepare another saturated solution of Ca(OH)2 (B).
2. To determine the hydroxide concentration in the saturated solution, a titration with
standardized HCl will be performed. Rinse a burette with about 5 mL of the HCl solution and
then fill the burette, making sure that there are no air bubbles trapped in the tip, and record the
initial liquid level in the burette. Using a digital pipette (or volumetric pipette), measure out
5.0 mL of the saturated Ca(OH)2 solution into a 125 mL Erlenmayer flask. Add one or two
drops of phenolphthalein indicator to this flask and you should see the solution’s colour change
to pink.. Titrate the Ca(OH)2 solution with the HCl solution, constantly swirling the flask,
until the pink colour just disappears (which means that the end-point is reached). Record the
final liquid level in the burette. Repeat this titration two more times.

3. You should now prepare a saturated solution of Ca(OH)2 at one higher temperature. using
solution (A) you should aim for a temperature somewhere between 60EC and 80EC; and
using (B) you should make a solution at the boiling point temperature. To prepare a
saturated solution of Ca(OH)2 at higher temperatures, your room temperature solution must
be heated on a hot plate.

a. To achieve the 60EC to 80EC temperature, place your flask on the hot plate, insert a
digital thermometer into the solution (holding the thermometer in place with a clamp)
and turn the hot plate on to a medium setting. Monitor the temperature as it is rising
and adjust the hot plate setting as required to achieve a temperature in the 60EC to
80EC. Try to maintain a stable temperature (+/- 1E) for about 5 minutes and record that
temperature.

b. To achieve the boiling point temperature, procede as in a. but using a higher setting on
the hot plate. Bring the solution to a boil and keep boiling for about 5 minutes. Record
the temperature of the boiling solution.

4. Your hot solution must now be filtered into another clean, dry 250 mL Erlenmayer flask. This
process must be done rapidly so that the temperature of the solution does not change
significantly. BE CAREFUL. THE FLASK IS VERY HOT AND MUST NOT BE
HELD IN YOUR BARE HAND. USE EITHER A HEAT RESISTANT GLOVE OR
 PAD OR A FIRM GRIPPING TONGS TO HANDLE THE HOT FLASK.

5. Turn off the hot plate.

6. Allow the solution to cool and then determine the hydroxide concentration as in Step 2. above

7. At the end of the lab, turn the heat and stir scales to minimum and unplug the power cord of
the heater/stirrer. Turn off the poser of the digital thermometer, wash and dry it. Decant all
chemical waste into the waste pails in the common fume hood. Wash all of the glassware
used, finishing with 3 distilled water rinses. Clamp the washed burette upside down and
open the stopcock. Return the 250 mL Erlenmayer flasks to the shared front bench. Return
other glassware to your locker.

Calculations USE BOTH YOUR DATA from (A) AND (B) FOR
THESE CALCULATIONS.
1. From the titration data, calculate the concentration of hydroxide in the saturated solution.
Knowing that when Ca(OH)2 dissolves, the resulting concentration of calcium ions is one half
the concentration of hydroxide, calculate the concentration of calcium ions. Use these values
to calculate the KSP of Ca(OH)2 . Do this calculation for each of the temperatures tested, room
temperature and the two higher temperatures measured by you and your partner.

2. From the equilibrium constant values, calculate the standard free energy change values.

3. From a plot of lnKSP vs 1/T, calculate the value of the standard enthalpy change and the
standard entropy change for the dissolving of Ca(OH)2 .

4. In your discussion, comment on the physical meaning of the results that you have calculated.
Name:______________________________ Student No.:___________________________
Lab Section No.:______________________
Pre-lab Questions

1. For a saturated solution of an unknown metal hydroxide, M(OH)2 , 13.94 mL of this solution
were required to neutralize 25.00 mL of 0.02 M HCl. Calculate the KSP of the metal
hydroxide.

2. Explain how the following equation will be made use of in the calculations for this
experiment. ÄGE = - RT lnK = ÄHE - T ÄSE
Name:______________________________
Lab Section No.:______________________ Student No.____________________________
Date:_________________________________
Data Sheet
Your Data

Solution (A) Trial Initial Burette Reading Final Burette Reading

Temperature . 1.

2.

3.

1.

2.

3.

Solution (B) temperature

1.

2.

3.
 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
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 ±Äx and ±Äy,

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

where Äx/x and Äy/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, Äz, 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:

equipment tolerance *

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

concentration of NaOH solution =

0.2631 g
______________ x 1________ x 1000 mL
________
204.22 g mol-1 27.93 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
 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. th

e solid + weighing bottle minus the mass of the weighing bottle. Each mass was uncertain

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

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

sum of the absolute value of

the deviation of each result
from the mean
precision = ± x 100%
(number of results) x (mean value)

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.

% 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.