TABLE OF CONTENTS

Page
General Laboratory Regulations, Safety Information, 2
Accuracy, Precision and Errors

Experiment 1: Gases: Exploring the Properties of Gases 11

Experiment 2: Reaction Kinetics: Kinetics of Hydrolysis of t-Butyl Chloride 15

Experiment 3 Reaction Kinetics: Kinetics of the Fading of Bromophenol Blue 17

Experiment 4: Reaction Kinetics: The Decomposition of Hydrogen Peroxide 20

Experiment 5: Reaction Kinetics: Rate Determination and Activation Energy 24

Experiment 6: Reaction Kinetics: The Rate and Order of a Chemical 28

Reaction

Experiment 7: Reaction Kinetics: The Base Hydrolysis of Ethyl Acetate 31

Experiment 8: Equilibrium: The Determination of an Equilibrium Constant 34

Experiment 9: Equilibrium: Determining Ka by the Half-Titration of a 39

Weak Acid

Experiment 10: Surface Chemistry: The Adsorption of Acetic Acid From an 42

Aqueous Solution by Charcoal.

Experiment 11: Thermodynamics: Enthalpy of Vapourization of Water 44

by Vapour Pressure Measurements

Experiment 12: Thermochemistry: Determining the Enthalpy ( H) of Some 46

Chemical Reactions

Experiment 13: Thermochemistry: The Enthalpy ( H) of Neutralization of 50

Phosphoric Acid

Experiment 14: Thermochemistry: Vapor Pressure and Heat of Vaporization 53

Experiment 15: Electrochemistry: Voltaic Cells 56

Experiment 16: Electrochemistry: Electroplating 60

Advanced Chemistry with Vernier
 GENERAL LABORATORY REGULATIONS AND SAFETY
INFORMATION

This course is designed to develop good laboratory techniques in the preparation, handling and
analysis of common substances as well as to illustrate some general chemical principles.
Emphasis is placed, where appropriate, on accuracy, understanding and on interpretation of
results.

Where possible you should be familiar with the experimental procedure before the laboratory
period, so that the time allocated for bench work is not wasted. In any event, the complete
instructions for an experiment should be read and understood before experimental work is
started. If in doubt, ask your lab supervisor – he/she is there to help you!

In some events, you may need to consult a relevant textbook for additional information to assist
you with the experimental write-up.

ATTENDANCE AT LABS
This is compulsory – poor attendance may require withdrawal from the Physical Chemistry
course. Absence due to illness must be substantiated by a medical certificate from your doctor or
a reputable medical care center, eg. the UTECH Health Centre.

WRITE-UP/ REPORTS
Reports should be written up and handed in exactly THREE DAYS after the date of the
experiment or as advised by your laboratory supervisor. Experiment will be written up in the
following order:
(i) Date:
(ii) Aim: This should be a brief statement of the purpose of the experiment.
(iii) Abstract: A short and concise overview of the experiment, technique employed, results
obtained and a brief comparison to known/literature data (if possible).
(iv) Introduction/Theory: A detailed descriptive and informative insight to the experiment.

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(v) Procedure: (Where appropriate) Give a brief account in your own words, of the procedure
you used in the experiment. USE THE PASSIVE VOICE AND THE PAST TENSE.
(vi) Results and Calculations: Where appropriate, clearly and neatly present your data in
tabular form. Give one sample calculation for each type of calculation. If many
calculations are performed, tabulate the results. Give all units and carry them through the
calculations. SI units should be used throughout. Theoretical values and other literature
values are provided in many textbooks. NB: Sometimes you have to search for them.
It is important to record any additional observations whether or not they appear pertinent
to the conclusion(s). Eg. transient colour changes not mentioned in the experimental
procedure given herein. Give fact, not conjecture.

(vii) Discussion and Conclusions: Provide a comprehensive interpretation and explanation of

your experimental results, eg. data trends, magnitude and meaning of calculated values,
any notable deviation from expected values, etc. Discuss the possible errors in your work.
From your experimental results draw as many conclusions possible. If students make
good evaluations of errors in a given experiment they will not lose as many marks, if
their results are bad, as they would if no evaluation was given.
(viii) Questions: Sometimes questions will be given at the end of an experiment. These
questions must be answered in your lab report/worksheet and will be marked as part of
the experiment.
(ix) References:
(x) Writing and presentation will be taken into account; however neatness, in itself, is less
important than legibility and clarity, which are of utmost importance.

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GENERAL LABORATORY INFORMATION

(a) Students may work in the laboratory only at times when a supervisor/technician is
present, and will only work in their particular laboratory period, unless permission is
given by the laboratory supervisors concerned.
(b) Each student is responsible for keeping his own work-bench in a clean and tidy condition.
Sinks must be kept clear of broken glasses and other solid waste (waste boxes are
provided under each bench).
(c) Reagent bottles must be left lying around the laboratory. They must be returned to the
stores or to the appropriate shelf.
(d) All students are requested to turn off gas, electricity and water as son as they are no
longer required.
(e) All balances must be carefully treated. The top-loading balances in the balance room
weigh to + 0.1 g and are used in preparative experiments as well as for rough initial
weighings for quantitative analysis. At no time must material be weighed out directly on
the pans or on filter paper. Any material accidentally spilled on them must be wiped off
immediately.
(f) Reagent bottles must never be taken into the balance room. Rough weighings must first
be done on the rough balances, and weighing containers must be used.
(g) Take very good care of your equipment. Students will be charged for the replacement of
damaged or missing equipment.
(h) Students are not alllowed in the Technician’s/Preparation room.
(i) No student should make any adjustment to electrical appliances or fixtures.
(j) Be alert to unsafe conditions and actions and call attention to them so that correction can
be made immediately.
(k) DO NOT SMOKE, EAT OR DRINK IN THE LABORATORY. Wash your hands
thoroughly with soap and water after leaving thelab.
(l) Avoid practical jokes or horseplay in the lab. Do not distract or startle any student.

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LABORATORY SAFETY PRECAUTIONS

All laboratories are hazardous places. Many solvents and reagents are highly inflammable, many
chemicals are corrosive or poisonous. Your personal safety in the laboratory largely depends on
your knowledge of possible dangers and on a strict adherence to proper safety procedures. Some
of these dangers and the ways to avoid them will be outlined here, others will be pointed out
later.

PROTECT YOUR EYES!!!!!

Work with acids, alkalis, and chemicals like bromine may be hazardous to your eyes. Be
particularly careful with caustic alkali it is exceedingly corrosive to eye tissue and even dilute
solutions are dangerous. ALL STUDENTS MUST HAVE AND WEAR A PAIR OF
GOGGLES OR SPECTACLES AT ALL TIMES WHEN IN THE LABORATORY.
People without eye protection will not be allowed to work in the laboratory. Goggles can be
purchased in the Department.

Some operations are particularly hazardous: thus, never place your eyes over the opening of any
chemical container (reaction flask, reagent bottle, etc.); Look at the container but never in it. If a
chemical should get into your eye, immediately wash it with PLENTY of clean water.

DRESS CODE

Clothing such as shorts, mini-skirts, sleeveless blouses, vests, as well as slippers or open top
shoes are NOT suitable to be worn in the laboratory. Tie up long hair, especially in the presence
of open flames. NB: Lab Safety Glasses and Labcoats MUST be worn at ALL TIMES during
laboratory sessions

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CHEMICAL PRECAUTIONS

(1) Regard all chemicals as poisons. Exercise care in handling all reagents, those known to
be corrosive. Nitric acid, bromine, concentrated sulphuric acid, concentrated sodium or
potassium hydroxide are common reagents which will cause painful skin damage in a
short time.
(2) Should any chemical come in contact with your skin, wash the area immediately with
plenty of soap and water, then deactivate any possible residual chemical by neutralization
or other chemical means. Follow this by a second thorough washing with soap and
water. Inform your supervisor about any accident of this nature.
(3) Never taste any chemical unless specifically instructed to do so. If you do ingest
anything, report it at once to the supervisor.

FIRE PRECAUTIONS

(1) Regard all liquids as flammable unless instructed otherwise, they should always be
heated in a water bath, not by a Bunsen burner.

(2) Solvents should always be kept in closed containers and never in open beakers. Keep
solvent containers well removed from open flames.

(3) Never pour flammable liquids from one container to another unless all flames nearby are
first extinguished: that means your neighbour’s as well as your own.

(4) never heat a closed apparatus assembly even if it includes a condenser in the system. The
increase in pressure due to heating may cause the assembly to burst or explode and, if a
flame is being used, any liquid present in the system may be ignited.

(5) Whenever an exothermic reaction is being carried out, prepare a cooling bath and
position the reaction vessel in such a way that the bath can be placed around it if the
reaction shows sign of getting out of control.

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(6) Avoid using flames in the laboratory whenever possible. If flames have to be used, light
a bunsen burner only when it is needed and extinguish the flame as soon as it is no longer
required.

(7) If, despite precautions, a fire does occur, it will usually be one that can be readily
confined and extinguished. However, it is essential that you remain calm and not extend
the fire in your haste to extinguish it. Minor fires may occur in beakers or flasks.
Covering the vessel with a gauze, watchglass or wet towel on order to exclude air may
usually smother such fires.

(8) Familiarize yourself with the location and operation of the nearest fire extinguisher,
which is used to smother bigger fires than in (7) with a blanket of carbon dioxide.

PRECAUTIONS IN HANDLING APPARATUS

(1) Never apply undue pressure or strain to any piece of glassware.

(2) Never use cracked or damaged glassware or glass rods that have not been fire polished.
A flask, which is cracked, may open if it is subsequently heated.
(3) Be careful when inserting glass tubing, thermometers, etc., into rubber bungs, heavy
rubber tubing or other resistant rubber items. If the glass slips, it can go a far way into
the hand, cut nerves and tendons and cause deep and nasty wounds.
(4) Glassware is most easily cleaned immediately after use. Most chemical residues can be
removed by washing the glassware with detergent and water. Wet dirt is much easier to
remove than dry dirt!

ACCIDENTS

(1) Minor accidents, like cuts and burns, are fairly common in the laboratory. Report them
to the supervisor, demonstrator or technician.
(2) Major accidents are handled similarly – report them to the supervisor, who will arrange
transport to the Health Center.

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WORKING IN THE LABORATORY

(1) Work carefully and steadily. Never hurry, since this invariably produces errors and
injuries, and do not run.

(2) Plan your work that you can be flexible in your approach; try to avoid bottlenecks, e.g.,
having to queue for distilled water or for chemicals and apparatus at the technician’s
window.

(3) Wherever possible, prepare each step of the experiment in advance so that apparatus and
chemicals are ready when required.

(4) Leave supply chemicals and general equipment in their proper places and in good order
for the next user.

(5) Do not remove chemicals, reagents solutions, etc., to your workbench; this both
inconveniences other students and clutters your working area.

(6) Clean equipment as soon as you have finished working with it. Never store dirty
equipment in your locker.

(7) Keep your working area clean and dry. Clean any spillage of chemicals, water, etc., they
occur.

(8) Do not climb on top of the workbenches or on laboratory stools.

MATHEMATICAL CONSIDERATIONS

Significant Figures

In the laboratory we make many kinds of measurements. The precision of the measurement
depends on the device we use to make it. Using an analytical balance, we can measure mass to
+ 0.0001 g, so if we have a sample weighing 2.4965 g, we have five meaningful figures in our
result. These figures are called reasonably enough, significant figures. If we measure the
volume of a sample using a graduated cylinder, the volume we obtain depends on the cylinder
we use. If we have a volume about 6 mL, and measure it with a 100 mL cylinder, we would
have difficulty distinguishing between volume of 6mL and 7 mL, and would be unable to say
more than that the volume was about 6mL. That volume contains only one significant figure.
With a 10 mL cylinder, we could measure the volume more precisely, report a volume of 6.4mL,

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and have confidence that both figures in our result were meaningful, and that it contained two
significant figures. Many measurements perhaps most, can be interpreted as we have here.
Sometimes it is not clear how many significant figures there are in a number. Say for example,
we are told to add 1mLof liquid from a pipet to a test tube. A pipette is a precisely made device,
and can deliver 1.00 mL of liquid if used properly. In such a case, it would be sensible to say
that there are really three (3) significant figures in that volume, rather than one. It would
probably have been better to be told to add 1.00 mL with a pipette, but often that is just not done,
even by the authors of this manual.

Some numbers are exact and have no inherent error. There will be an integral number, like 12,
or 19, students in the lab. There is no way there will be 14.5 students unless there is something
strange going on. Conversion factors, used to convert one set of units to another, often contain
exact numbers: 1 meter = 100 cm. Both numbers are exact, with no error at all. With volumes,
1 liter = 1000 mL. Again both numbers are exact. If we convert from one system to another,
then usually only one of the numbers in the conversion factor is exact: 1 mole = 6.022 × 1023
molecules. Here the 1 is exact, but the second number is not, and has four significant figures.

If you are in doubt as to the number of significant figures in a given number, there is a method
for finding out that usually works. We write the number in exponential notation, expressing the
number as the product of a number between 1 and 10 times a power of ten.

26.042 = 2.6042 × 101; 0.0091 = 9.1 × 103; 605.20 = 6.0520 × 102

The first number in the product has the number of significant figures we seek. So, the first of the
above number has 5 significant figures; the second has 2, and the third has 5 (a trailing zero is
significant). There is no problem with this approach, and that is that sometimes we are given a
number with no decimal point, like 2400. We cannot be sure how many significant figures are in
that number, since, if the number was rough, there might be 2, but there could be 4 or even more.
Here, you have to use some judgment, but in the absence of any guide, you would choose 4.

Students usually have little trouble deciding on the number of the significant figures in a piece of
data. The difficulty arises when the piece of data is used in a calculation, and they have to

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express the result using the proper number of significant figures. Say for example, you are
weighing a sample in a beaker and you find that:

Mass of sample plus beaker = 25.4329g

Mass of beaker = 24.6263g
Mass of sample = 0.7066g

Even though the two measured masses contain 6 significant figures, the mass of the sample
contains only 4. In another case, where we mix some components to make a solution, weighing
each of the components separately on different balances, so we get:

Mass of beaker = 25.5329 g

Mass of water = 14.0 g
Mass of salt = 6.42 g
Total mass = ?
Here we have several pieces of data, each with a different degree of precision. The first mass is
good to 0.0001g, the second to 0.1g and the third to 0.01g. If we take the sum, we get 46.9529g,
but we certainly can’t report that value, since it could be off, not by 0.0001g, but by 0.1g, the
possible error in the mass of the water.

We can’t improve the quality of a result by a calculation, so, using good sense, we can only
report mass to + 0.1 g. Since the measured mass is closer to 47.0 g than to 46.9 g, we round up
47.0 g as the reported mass, and have a mass with 3 significant figures. Generalizing, in adding
or subtracting numbers, round off the result so that it has the same number of decimal places as
there are in the measured quantity with the smallest number of decimal places. Round off the
last digit up if the number that follows is greater than 5, and don’t round up if it is not.
When multiplying or dividing measured quantities, the rule is quite simple: the number of
significant figures in the result is equal to the number of significant figures in the quantity with
the smallest number of significant figures. Consult your text for further details.

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TYPES OF ERRORS

Evaluation of Analytical data

All physical measurements are subject to some degree of uncertainty. For example, if we
weighed a beaker on a top loading balance we may get a value of 15.7 g. This tells us that the
beaker weighs between 15.7 g and 15.8 g. If we now reweigh the beaker using a more accurate
balance we may get 15.7151. Again assuming faultiness weighing and balance, we see that now
we have narrowed the error in weighing from 0.1 g in the first case to 0.0001 g in the second.

No matter how much we improve our measuring methods we can never attain a perfect
measurement. The best we can do is to make sure that we know what the probable error in the
measurement is and how it will affect the conclusions we are trying to draw from the
measurement.

Errors in any set of measurements can be divided into two classes:

(ii) Determinate or systemic errors
(iii) Indeterminate or Random errors

Determinate Errors

Determinate Errors are those, which have a definite value and assignable cause in principle
though not always in practice. Determinate errors produce that are consistently too high or too
low, and usually differ from the true value by a definite amount. These errors arise from faults in
experimental design or execution, improper calibration, failure to control conditions such as
temperature, mathematical blunders, personal errors in reading scales or colours, incomplete
reactions and any other causes of errors which tend to remain roughly the same in sign and
magnitude when the experiment is repeated. Elimination and evaluation of determinate errors
requires meticulous experimental design, calibration, use of controls and blanks etc. and general
improvement in the technique being used by the experimenter, eg. minimize this type of error by
using a temperature control water bath when carrying out an experiment which is temperature
dependent.

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Indeterminate Errors

As the name implies, indeterminate errors come from unknown causes and are not control by the
experimenter. Because of their unpredictability, indeterminate errors include limitations of
scale-readings, noise in electrical circuits etc. It is assumed that they are composite errors arising
from a variety of causes and are just as likely to be greater as less than the true value; their sign
and magnitude are due purely to chance. Indeterminate errors may in principle be reduced by an
arbitrary factor by taking and averaging a sufficiently large number of independent
measurements, eg. by doing a few titration measurements to obtain one average volume.

The statistical treatment of indeterminate/random errors is very well established and this allows
one to estimate the limits of indeterminate error in any data collected. Determinate errors cannot
be described in terms of a tidy mathematical theory.

Precision and Accuracy in Measurement

Although in everyday language precision and accuracy are often used interchangeably, they
have different meanings.
Precision refers to the agreement between repeated determinations of a physical quantity
measured under identical conditions.
Several methods exist for expressing the precision data; among these are the deviation from the
mean and the standard deviation, which will be discussed later.
The accuracy of a determination is a measure of the agreement between the obtained
results and the “true” value. The accuracy of a measurement is often described in terms of the
absolute error (E) which is the difference between the observed the observed value xi and the
accepted value xt, i.e.

E = xi - xt

It can also be expressed as the relative error which is expressed as a percentage of the accepted
value.
Relative error = (xi - xt)/xt

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The accuracy of a result is an expression of the total uncertainty including that due to systematic
errors.
NOTE : It is possible for a set of data to have high precision but low accuracy.
Evaluation of Random Errors
Repeated measurements of a quantity will seldom be exactly the same. It is therefore necessary
to select a central “best” value for the set of data as this will be more reliable than any of the
individual measurements.

The mean is one quantity, which can serve as the central value. The mean or average (x) is the
numerical value obtained by the dividing the sum of replicate measurements by the number of
individual results in the set (n).

Mean = x = xi/ n
i=1

e.g. the mean of 10.06, 10.20, 10.08, 10.10 is:

mean = (10.06 + 10.20 + 10.08 + 10.10)/ 4 = 10.11

Mean Deviation and Standard Deviation

The deviation from the mean (x – xi) is a common method for describing precision and this is the
numerical difference without regard to sign between the experimental value (xi) and the mean for
the set of data that includes the value. For example, the analysis for the percent chloride in a
sample yielded the following results:

Sample Percent chloride (%) Deviation from mean xi - x

x1 24.39 0.055
x2 24.19 0.145
x3 24.36 0.025
x4 24.40 0.065

97.34 0.290

x(mean) = 24.34 %

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The average deviation is a useful precision index and is defined as:

Average deviation = (x – xi)/ n

Although very widely used, the average deviation is used only for qualitative comparisons. It is
quite sensitive to the sample size.
The standard deviation (S) is the most widely used and the most convenient measure of
precision.

S = { (x – xi)2/ (n - 1}

The relative standard deviation is S/x and this is frequently expressed as a percentage. One
represents the experimentally determined value and its standard deviation as y S

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 Exploring the Properties of Gases

Experiment 1: Vernier #30

The purpose of this investigation is to conduct a series of experiments, each of which illustrates a
different gas law. You will be given a list of equipment and materials and some general
guidelines to help you get started with each experiment. Four properties of gases will be
investigated: pressure, volume, temperature, and number of molecules. By assembling the
equipment, conducting the appropriate tests, and analyzing your data and observations, you will
be able to describe the gas laws, both qualitatively and mathematically.

OBJECTIVES
In this experiment, you will
Conduct a set of experiments, each of which illustrates a gas law.
Gather data to identify the gas law described by each activity.
Complete the calculations necessary to evaluate the gas law in each activity.
From your results, derive a single mathematical relationship that relates pressure, volume,
temperature, and number of molecules.

MATERIALS
Vernier computer interface large-volume container for water bath (at least
computer 10 cm in diameter and 25 cm high)
Vernier Gas Pressure Sensor 125 mL Erlenmeyer flask
Temperature Probe hot-water supply (up to 50°C) or hot plate
20 mL gas syringe ice
plastic tubing with two Luer-lock connectors 100 mL graduated cylinder
rubber stopper assembly with two-way valve

PRE-LAB EXERCISE
Review each of the four parts of this experiment before starting your work. You will need to
decide the best way to conduct the testing, so it is wise to make some plans before you begin.
You may wish to conduct a test run without collecting data, in order to observe how the
experiment will proceed.

In each part of the experiment, you will investigate the relationship between two of the four
possible variables, the other two being constant. In this pre-lab exercise, sketch a graph that
describes your hypothesis as to the mathematical relationship between the two variables; e.g.,
direct relationship or inverse relationship.

Part I Pressure, P, and volume, V (temperature and number of molecules constant).

Part II Pressure, P, and absolute temperature, T (volume and number of molecules constant).
Part III Volume, V, and absolute temperature, T (pressure and number of molecules constant).
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Part IV Pressure, P, and number of molecules, n (volume and absolute temperature constant).

PROCEDURE
Part I Pressure and Volume
1. Obtain and wear goggles.

2. Position the piston of a plastic 20 mL syringe so that there will be a measured volume of air
trapped in the barrel of the syringe. Attach the syringe to the valve of the Gas Pressure
Sensor, as shown in Figure 1. A gentle half turn should connect the syringe to the sensor
securely. Note: Read the volume at the front edge of the inside black ring on the piston of the
syringe, as indicated by the arrow in Figure 1.

Figure 1

3. Connect the Gas Pressure Sensor to Channel 1 of the Vernier computer interface. Connect
the interface to the computer using the proper cable.

4. Start the Logger Pro program on your computer. Open the file “30a Gases” from the
Advanced Chemistry with Vernier folder. This file allows you to collect pressure data from
the Gas Pressure Sensor, using Events with Entry mode. For each pressure reading you take
with a button, this mode lets you enter a volume value.

5. Measure the pressure of the air in the syringe at various volumes. Print a copy of the graph
and data. The best results are achieved by collecting at least six data points.

Part II Pressure and Absolute Temperature

In this experiment, you will study the relationship between the absolute temperature of a gas
sample and the pressure it exerts. Using the apparatus shown in Figure 2, you will place an
Erlenmeyer flask containing an air sample in a water bath and you will vary the temperature of
the water bath.

6. Connect the Gas Pressure Sensor to Channel 1 and a Temperature Probe to Channel 2 of the
interface.

7. Assemble the apparatus shown in Figure 2. Be sure all fittings are airtight. Make sure the
rubber stopper and flask neck are dry, then twist and push hard on the rubber stopper to
ensure a tight fit.

8. Open the file “30b Gases” from the Advanced Chemistry with Vernier folder. This file is set
up to collect pressure and temperature data from the attached sensors, using Selected Events
mode. This mode allows you to collect a data pair simultaneously from the Gas Pressure
Sensor and Temperature Probe by clicking on the button.

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 Figure 2

9. Collect pressure data at several different temperatures. Set up water baths in the large-volume
container, as you need to. Print a copy of the graph and data.

Part III Volume and Absolute Temperature

In this experiment, you will study the relationship between the volume of a gas sample and its
absolute temperature. Using the apparatus shown in Figure 3, you will place an Erlenmeyer flask
containing an air sample in a water bath and you will vary the temperature of the water bath.
Keep some of these factors in mind as you plan your procedure.
If you are starting with a cold-water bath, set the piston at the 0 mL mark on the syringe. This
will allow the gas volume to be increased in warmer water baths.
The temperature of the water bath cannot be increased by more than 30-40 degrees from your
starting temperature.
Even though you are not plotting pressure, it is important to monitor pressure in the Meter to
ensure that it remains constant.
It is important to know the total volume of air in the flask and the syringe. The volume of the
flask, up to the bottom of rubber stopper, can be accurately measured using a graduated
cylinder. For the estimated volume of the tubing (from the rubber stopper to the Gas Pressure
Sensor box), as well as in the valve below the bottom of the syringe, use a value of ~4 mL.
10. Ensure that the Gas Pressure Sensor is plugged into to Channel 1 and the Temperature Probe
is plugged into Channel 2 of the interface.

11. Assemble the apparatus shown in Figure 3. Be sure all fittings are air-tight. Make sure the
rubber stopper and flask neck are dry, then twist and push hard on the rubber stopper to
ensure a tight fit. Be sure the water level is at least as high as the confined air in the syringe.

Figure 3

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12. Open the file “30c Gases” from the Advanced Chemistry with Vernier folder. This file is set
up to collect pressure and temperature data from the attached sensors, using Events with
Entry mode. This mode allows you to collect a data pair simultaneously from the Gas
Pressure Sensor and Temperature Probe by clicking on the button and entering a
value for the volume. Even though the pressure reading will not be plotted on the graph of
volume vs. temperature, it is important for pressure to be monitored so that it can be kept
constant.

13. Collect volume data at several different temperatures. Set up water baths in the large-volume
container as you need them, ranging from ice water to hot water. Print a copy of the graph
and data.

Part IV Pressure and Number of Molecules

In this experiment, you will study the relationship between the number of molecules in a gas
sample and the pressure it exerts.
You can use the same setup as in the previous trial, although the water bath and Temperature
Probe are optional. (Temperature must be constant, so choose a convenient temperature to
run the experiment.)
You might be wondering how you are going to count molecules for this section. Here is a
hint. Avogadro’s hypothesis states that, “Equal volumes of gases, at the same temperature
and pressure, contain equal numbers of molecules.” Therefore, if you keep the temperature
and volume constant during the experiment, you can assume that gas volumes are
proportional to numbers of molecules. Instead of entering a total number of molecules, you
could enter a total volume of gas that has been compressed into the flask. For example, 120
mL worth of molecules could be entered as 120 molecules, 140 mL worth of molecules
would be entered as 140 molecules.)
14. Ensure that the Gas Pressure Sensor is plugged into Channel 1 of the interface.

15. Open the file “30d Gases” from the Advanced Chemistry with Vernier folder. This file allows
you to collect data from the Gas Pressure Sensor by clicking on the button and
entering a value for the number of molecules.

16. Collect pressure data with several different numbers of molecules introduced into the system.
Print a copy of the graph and data.

DATA ANALYSIS
1. For each of the four parts of the experiment, write an equation using the two variables and a
proportionality constant, k (e.g., for Part I, P = k V if direct, or P = k/V if inverse).

2. Calculate the constant, k, for each of the four gas laws that you tested. This value can be an
average for each of the data pairs in each part of the experiment.

3. Based on the mathematical relationship and equation that you obtained in Step 1 above for
each part of the experiment, combine all four variables into a final equation. This “combined
equation” will contain P, T, V, and n, as well as a new proportionality constant, K. Be sure to
explain how you obtained your result (how you combined the equations).

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Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Results and Calculations (Data Analysis) 7
Discussion (include answers to questions) 6
Conclusion 1
References 1
Total = 20 marks

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 KINETICS OF HYDROLYSIS OF t-BUTYL
CHLORIDE
Experiment 2
OBJECTIVE
1. To Investigate the Rate of Hydrolysis of t-Butyl Chloride.

INTRODUCTION
The rate of a chemical reaction can be determined by measuring the variation with time of some
physical parameter, which depends upon concentration e.g. absorbance, electrical conductivity.
The rate constant for a first order reaction will be determined by measuring changes in
conductivity. Measurements at more than one temperature enable the activation energy and A
factor for the reaction to be found.

Tertiary butyl chloride reacts with water according to the stoichiometric equation:
(CH3)3CC1 + 2H2O (CH3)3 COH + H3O+ + C1–

H3O+ and C1- of the reactants and products contribute significantly to be the electrical
conductivity of the solution, and hence measurement of conductance can be used to follow the
progress of the reaction. The rate of reaction is given by
-d [t-buC1] /dt = d ([H3O+] + [C1–])/dt = k [t-BuC1]
(1)
and you are being asked to verify this. If the conductances of the solution at times 0, t and are
respectively G0, Gt, G then the concentration of H3O+ and C1- at times t and are given by

([H3O+] + [C1-])t α Gt – G0
(2)

([H3 O+] + [C1-]) α G - G0

(3)
Equation 4 describes the reaction with stoichiometry A B and which is found to be first
order in A

ln ([B] - [B]0/([B] - [B] = kt

(4)
where [B]0, [B] are the concentrations of B times 0, t and respectively, hence

ln [(G - G0) / (G - Gt)] = kt or ln [ (G - Gt ) / (G - G0) ] = -kt

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so that here a plot of ln (G - Gt) against t should be linear with slope -k.

APPARATUS & CHEMICALS

t-butyl chloride (2-chloro-2-methyl propane) 5 cm3; Acetone (300 cm3) ; Conductivity meter;
three 150 cm3 beakers, pipette.

EXPERIMENTAL
Place in the thermostatted water bath provided a beaker containing 80 cm3 of 20:80 v/v
acetone/water solvent. Immerse the conductivity electrode assembly in the beaker while stirring
the solution constantly. Allow at least 15 minutes for thermal equilibration before starting the
run. The table shows the total period over which measurements should taken.

Run T/˚C t-BuC1/cm3 tfinal /min

1 25 1.0 15
2 35 1.0 3
Readings should be taken initially every 15 seconds and then every 45 seconds for run 1 and
every 15 seconds run 2. For all of the runs set the conductance meter range switch to 10-3 Ohm-1.
Runs 1, and 2 begun by injecting the sample from a pipette (use a bulb filler) and simultaneously
starting a stopwatch.

Results
1. For all the runs, plot the conductance, G, against time and estimate the value G at
completion of the reaction.
2. Plot ln(G -Gt) against and hence find the rate constant k.
3. Evaluate the activation energy Ea

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Results and Calculations (Data Analysis) 7
Discussion (include answers to questions) 6
Conclusion 1
References 1
Total = 20 marks

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Adapted from UWI Physical Chemistry Manual---C23J

KINETICS OF THE FADING OF

BROMOPHENOL BLUE
Experiment 3

OBJECTIVES
To investigate the reaction of Bromphenol Blue in basic medium and to the calculate its first
order rate constant.

INTRODUCTION
Spectrophotometry is a useful tool to follow the progress of chemical reactions. Beer’s Law I
shows that the intensity of light transmitted at a particular wavelength by a particular solution is
given by the equation.
- cl
I = (Io) 10 (1)
Where (I0) is the incident light intensity, is the molarity extinction coefficient of the absorber
at the given wavelength for the light through the solution.
When the logarithms of the above equation is taken we get equation 2,
Log [Io) /I] = cl = A (2)
where A is called “Absorbance” or “Optical density”
The absorbance is proportional, for a given wavelength and path length to the concentration;
therefore, the absorbance can be measured directly.

Structure I, Bromophenol blue, BB, is a dye of the triphenylmethan type, which exists in only
acid solution.

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At progressively higher values of pH, the anion II, the dianion of III, and finally the trianion of
IV successively become the important form of the dye.

The change anion to dianion is accompanied by a strong colour change. The trianion is
colourless – the indicator fades at high pH.

At the pH of this experiment, the equilibrium constant for the fading of BB, k1/k-1, is very large
and the reaction may, therefore, be considered as being irreversible. Additionally, the molar
extinction coefficient as large enough for the reaction to be followed spectrophotometrically.

If the reaction is first-order in BB,

k1t = ln([BB]0/[BB]t) where (BB)0 and (BB)t are the

Concentrations of BB at t =0
and t = t respectively.

Let A0, and A be the absorbance values of a fading Bb solution at t = 0, t = t and t = infinity
respectively. Then:

(BB)0 is proportional to (A0 - A and

(BB)t is proportional to (At- A ) and
ln (At-A ) = ln (A0-A ) – k1t

EXPERIMENTAL
Apparatus & Chemicals
Spectronic spectrophotometer. Stopwatch. Graduated 5 cm3 pipette. 10 cm3 pipette. Cuvettes.
Thermometer. 50 cm³ burette. Conical flask for titration.

5 ×10-4 M bromophenol blue, 0.25 M NaOH. Potassium hydrogen phthalate & Phenolphtalein.

Preliminary Measurements
Equilibrate the solutions at room temperature then record this temperature.
The NaOH soution should the be standardize against weighed amounts of potassium hydrogen
phthalate.

Zero the spectrophotometer with reference solutions (blanks) by adding 2 parts of water to 100
parts of base.

Ask a Demonstrator to show you how to measure absorbance.

You will need to find the wavelength of maximum absorption for the dianion because that is the
wavelength at which the reaction is most easily monitored. To a small sample of stock BB the

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base is added drop wise until it just turns blue (pH about 4.6). Locate max for this sample with
the spectrophotometer. (dilute the solution with water before finding max).

Kinetic Runs
Make a 2:1000 dilution of the stock BB with base ( this should be done quickly and accurately)
and measure the absorbance. Start the stopwatch and record the absorbance at about 3 minutes
intervals over a period of at least 5 half-lives, or 60 mins which ever is less. Retain the reaction
mixture and take the t = infinity reading the next day.

CALCULATIONS
Tabulate t, At, (At - A ), ln(At - A ) for each reaction run and obtain k1 from the plot of versus t.

EXERCISE
1. Assuming an Arrhenius activation energy of 60 kJ mol-1 calculate how much the rate
will increase if the temperature in increased to 2 K above room temperature. Within
this context comment on the temperature control in your experiments.

2. Explain why there is a strong colour change in going from II to III (anion to
dianion).

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Results and Calculations (Data Analysis) 7
Discussion (include answers to questions) 6
Conclusion 1
References 1
Total = 20 marks

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Adapted from UWI Physical Chemistry Manual---C23J

The Decomposition of
Hydrogen Peroxide
Experiment 4: Vernier # 12

The decomposition of hydrogen peroxide in aqueous solution proceeds very slowly. A bottle of
3% hydrogen peroxide sitting on a grocery store shelf is stable for a long period of time. The
decomposition takes place according to the reaction below.
2 H2O2 (aq) → 2 H2O (l) + O2 (g)
A number of catalysts can be used to speed up this reaction, including potassium iodide,
manganese (IV) oxide, and the enzyme catalase. If you conduct the catalyzed decomposition of
hydrogen peroxide in a closed vessel, you will be able to determine the reaction rate as a function
of the pressure increase in the vessel that is caused by the production of oxygen gas. If you vary
the initial molar concentration of the H2O2 solution, the rate law for the reaction can also be
determined. Finally, by conducting the reaction at different temperatures, the activation energy,
Ea, can be calculated.

OBJECTIVES
In this experiment, you will
Conduct the catalyzed decomposition of hydrogen peroxide under various conditions.
Calculate the rate constant for the reaction.
Determine the rate law expression for the reaction.
Calculate the activation energy for the reaction.

Figure 1
MATERIALS
Vernier computer interface 3 % hydrogen peroxide, H2O2, solution
computer 0.5 M potassium iodide, KI, solution
Vernier Gas Pressure Sensor 18 150 mm test tube
thermometer or Temperature Probe two 10 mL graduated cylinders
one-hole rubber stopper with stem graduated plastic Beral pipet
tubing with two Luer-lock connectors 1 liter beaker
solid rubber stopper (#1) ~800 mL room temperature water
distilled water
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PRE-LAB EXERCISE
The hydrogen peroxide solution that you are using in this experiment is labeled as a 3 %
solution, mass/volume. However, in order to complete the calculations, the concentration must
be in molarity. Calculate the molarity of a 3 % mass/volume H2O2 solution (Part I, II, and IV)
and a 1.5 % mass/volume H2O2 solution (Part III) and record these values in the table below.

Volume H2O2 [H2O2] Volume KI [KI]

Part
(mL) before mixing (mL) before mixing
I 4 1 0.50 M
II 4 1 0.25 M
III 4 1 0.50 M
IV 4 1 0.50 M

PROCEDURE
Part I Decompose 3% H2O2 solution with 0.5 M KI solution at ~20°C.
1. Obtain and wear goggles.

2. Prepare the reagents for temperature equilibration.

a. Obtain room temperature water to set up a water bath to completely immerse the test
tube. Use a thermometer or a Temperature Probe to measure the temperature of the bath.
Record this temperature in your data table for Parts I-III; presume that the water bath
temperature remains constant throughout.
b. Measure out 4 mL of 3 % H2O2 solution into the test tube. Seal the test tube with the solid
rubber stopper and place the test tube in the water bath.
c. Measure out 2 mL of 0.5 M KI solution in a graduated cylinder. Draw about 1 mL of the
KI solution into a graduated Beral pipet. Invert the pipet and immerse the reservoir end of
the pipet in the water bath.
3. Connect a Gas Pressure Sensor to Channel 1 of the Vernier computer interface. Connect the
interface to the computer using the proper cable.

4. Use the plastic tubing to connect the one-hole rubber stopper to the Gas Pressure Sensor, as
shown in Figure 1. About one-half turn of the fittings will secure the tubing tightly.

5. Start the Logger Pro program on your computer. Open the file “12 Peroxide” from the
Advanced Chemistry with Vernier folder.

6. Prepare to run the reaction and collect pressure data.

a. Remove the test tube from the water bath and remove the solid stopper.
b. Remove the plastic Beral pipet from the water bath and quickly transfer 1 mL of KI
solution into the test tube. Tap or lightly shake the test tube to mix the reagents.
c. Seal the test tube with the one-hole stopper connected to the Gas Pressure Sensor.
d. Place the test tube back in the water bath.
7. Click to begin data collection. Data will be gathered for three minutes. If necessary,
gently hold the test tube so that it stays completely immersed in the water bath.
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 8. When the data collection is complete, carefully remove the stopper from the test tube to
relieve the pressure. Dispose of the contents of the test tube as directed.

9. Examine the graph of Part I. Select a linear region just beyond the initial flat portion of the
graph that covers one minute of the reaction. Click the Linear Regression button, , to
calculate the best-fit line equation. Record the slope as the initial rate of the reaction in your
data table. Store the results from the first trial by choosing Store Latest Run from the
Experiment menu.

10. Rinse and clean the test tube for the second trial.

Part II Decompose 3% H2O2 solution with 0.25 M KI solution at ~20°C

11. Measure out 4 mL of 3 % H2O2 solution into the test tube. Seal the test tube with the solid
rubber stopper and place the test tube in the water bath.

12. Add 1 mL of distilled water to the remaining 1 mL of KI solution in the graduated cylinder.
Swirl the mixture gently to mix the solution.

13. Draw 1 mL of the KI solution into a plastic Beral pipet. Invert the pipet and immerse the
reservoir end of the pipet in the water bath. Allow both the test tube and the Beral pipet to
remain in the water bath for at least two minutes before proceeding.

14. Repeat Steps 6-10 to complete Part II. Remember to store the data.

Part III Decompose 1.5% H2O2 solution with 0.5 M KI solution at ~20°C
15. Prepare a 1.5 % H2O2 solution by mixing 2 mL of distilled water with 2 mL of 3 % H2O2
solution. Transfer the resulting 4 mL of the 1.5 % H2O2 solution to the test tube, seal the test
tube with the solid stopper, and place the test tube in the water bath.

16. Rinse and clean the graduated cylinder that you have used for the KI solution. Add a fresh 2
mL of 0.5 M KI solution to the graduated cylinder.

17. Draw 1 mL of the KI solution into a plastic Beral pipet. Invert the pipet and immerse the
reservoir end of the pipet in the water bath. Allow both the test tube and the Beral pipet to
remain in the water bath for at least two minutes before proceeding.

18. Repeat Steps 6-10 to complete Part III, and store the data.

Part IV Decompose 3% H2O2 solution with 0.5 M KI solution at ~30°C

19. Conduct Part IV identically to the procedure in Part I, with one exception: set the water bath
at 30°C.

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DATA TABLE

Temperature Initial rate

Part Reactants
(°C) (kPa/s)

I 4 mL 3.0% H2O2 + 1 mL 0.5 M KI

II 4 mL 3.0% H2O2 + 1 mL 0.25 M KI

III 4 mL 1.5% H2O2 + 1 mL 0.5 M KI

IV 4 mL 3.0% H2O2 + 1 mL 0.5 M KI

DATA ANALYSIS
–
Initial rate [H2O2] [I ] Rate constant
Part
(mol/L-s) after mixing after mixing k
I

II
III

IV

1. Calculate the rate constant, k, and write the rate law expression for the catalyzed
decomposition of hydrogen peroxide. Explain how you determined the order of the reaction
in H2O2 and KI.

2. The following mechanism has been proposed for this reaction:

H2O2 + I– → IO– H2O

H2O2 + IO– → I– + H2O + O2
If this mechanism is correct, which step must be the rate-determining step? Explain.

3. Use the Arrhenius equation (shown below) to determine the activation energy, Ea, for this
reaction.
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 k1 Ea 1 1
ln
k2 R T2 T1

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Prelab Exercise 2
Results: Data 4
Data Analysis (4 + 2 + 2) = 8
Discussion (include answers to questions) 4
Conclusion 1
References 1_______
Total = 25 marks

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 Rate Determination
and Activation Energy

Experiment 5: Vernier # 35

An important part of the kinetic analysis of a chemical reaction is to determine the activation
energy, Ea. Activation energy can be defined as the energy necessary to initiate an otherwise
spontaneous chemical reaction so that it will continue to react without the need for additional
energy. An example of activation energy is the combustion of paper. The reaction of cellulose
and oxygen is spontaneous, but you need to initiate the combustion by adding activation energy
from a lit match.
In this experiment you will investigate the reaction of crystal violet with sodium hydroxide.
Crystal violet, in aqueous solution, is often used as an indicator in biochemical testing. The
reaction of this organic molecule with sodium hydroxide can be simplified by abbreviating the
chemical formula for crystal violet as CV.
CV+(aq) + OH–(aq) → CVOH(aq)
As the reaction proceeds, the violet-colored CV+ reactant will slowly change to a colorless
product, following the typical behavior of an indicator. The color change will be precisely
measured by a Vernier Colorimeter (see Figure 1) set at 565 nm wavelength. You can assume
that absorbance is directly proportional to the concentration of crystal violet according to Beer’s
law.
The molar concentration of the sodium hydroxide, NaOH, solution will be much greater than the
concentration of crystal violet. This ensures that the reaction, which is first order with respect to
crystal violet, will be first order overall (with respect to all reactants) throughout the experiment.
You will monitor the reaction at different temperatures, while keeping the initial concentrations
of the reactants the same for each trial. In this way, you will observe and measure the effect of
temperature change on the rate of the reaction. From this information you will be able to
calculate the activation energy, Ea, or the reaction.

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OBJECTIVES
In this experiment, you will
React solutions of crystal violet and sodium hydroxide at four different temperatures.
Measure and record the effect of temperature on the reaction rate and rate constant.
Calculate the activation energy, Ea, for the reaction.

Figure 1

MATERIALS
Vernier computer interface 1 liter beaker
computer ice
Vernier Colorimeter two 10 mL graduated cylinders
Temperature Probe two 100 mL beakers
5 plastic cuvettes 50 mL beaker
0.10 M sodium hydroxide, NaOH, solution watch with a second hand
2.5 × 10–5 M crystal violet solution

PROCEDURE
1. Obtain and wear goggles.

2. Connect a Colorimeter to Channel 1 of the Vernier computer interface. Connect a

Temperature Probe to Channel 2. Connect the interface to the computer with the proper
cable.

3. Start Logger Pro on your computer. Open the file “35 Activation Energy” from the Advanced
Chemistry with Vernier folder.

4. Set up and calibrate the Colorimeter. Note: You will use this calibration for all four trials in
this experiment. Follow these steps to calibrate the Colorimeter.
a. Prepare a blank by filling an empty cuvette ¾ full with distilled water. Place the blank in
the cuvette slot of the Colorimeter and close the lid.
b. If your Colorimeter has a CAL button, set the wavelength on the Colorimeter to 565 nm,
press the CAL button, and proceed directly to Step 5. If your Colorimeter does not have a
CAL button, continue with this step to calibrate your Colorimeter.
c. Choose Calibrate  CH1: Colorimeter (%T) from the Experiment menu and then click
.
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 d. Turn the wavelength knob on the Colorimeter to the “0% T” position.
e. Type “0” in the edit box.
f. When the displayed voltage reading for Reading 1 stabilizes, click .
g. Turn the knob of the Colorimeter to the Green LED position (565 nm).
h. Type “100” in the edit box.
i. When the voltage reading for Reading 2 stabilizes, click , and then click .
5. Prepare a cool water bath, ~10°C, in a 1 liter beaker. The bath can be shallow because you
will be using it to cool the two 10.0 mL aliquots of reactants. Immerse the tip of a
Temperature Probe in the cool water bath.

6. Ready the NaOH and crystal violet solutions for the first trial.
a. Use a 10 mL graduated cylinder to obtain 10.0 mL of 0.10 M NaOH solution. Transfer
the solution to a 100 mL beaker. CAUTION: Sodium hydroxide solution is caustic.
Avoid spilling it on your skin or clothing.
b. Use another 10 mL graduated cylinder to obtain 10.0 mL of 2.5 × 10–5 M crystal violet
solution. Transfer the solution to a second 100 mL beaker. CAUTION: Crystal violet is a
biological stain. Avoid spilling it on your skin or clothing.
c. Place the two 100 mL beakers of reactants in the water bath. Make sure that the level of
the solutions on the beakers is below the level of the water bath. The beakers should be in
this water bath for at least one minute.
7. Conduct the first trial. Be ready to time the reaction.
a. Check the temperature of the water bath; it should be holding steady at or near 10°C.
b. When you are certain that the reactants have been cooled to ~10°C, pour the NaOH and
crystal violet solutions into the 50 mL beaker. Start timing the reaction using the second hand
on your watch. You will allow the reaction to run for one minute before proceeding to Part c
of this step. Stir the reaction mixture with the Temperature Probe.
c. After one minute, record the temperature of the mixture.
d. Fill a clean, dry cuvette about ¾ full with the reaction mixture. Place the cuvette in the
Colorimeter. Close the lid on the Colorimeter.
e. Click to begin collecting absorbance data.
f. Collect data for 60 seconds. Observe the progress of the reaction in the beaker.
g. When data collection is complete, carefully remove the cuvette from the Colorimeter.
Dispose of the contents of the beaker and cuvette as directed.
8. Because the reaction is first order with respect to crystal violet, you can determine the rate
constant, k, by plotting a graph of ln Absorbance vs. time.
a. Choose New Calculated Column from the Data menu.
b. Enter “ln Absorbance” as the Name, and leave the unit blank.
c. Enter the correct formula for the column into the Equation edit box by choosing “ln” from
the Function list, and selecting “Absorbance” from the Variables list. Click .

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 d. Click on the y-axis label. Choose ln Absorbance. A graph of ln absorbance vs. time
should now be displayed.
e. Click the Linear Regression button, . From the slope value, determine the rate constant,
k, and record it in your data table.
f. Close the Linear Regression box by clicking the X in the corner of the box.
9. To prepare to collect data for another trial, choose Store Latest Run from the Experiment
menu. For the next trials that you do, you will monitor the progress of the reaction on the
graph of ln absorbance vs. time.

10. You are now ready to perform another trial. The next trials will be at ~15°C, ~20°C, and
~25°C.
a. Prepare the next water bath, ~15°C, by adding warm water to the 1 liter beaker.
b. Add 10 mL of NaOH and 10 mL of crystal violet solutions to their respective 100 mL
beakers, and lower them into the water bath as you did before.
c. When you are certain the reactants have cooled to the temperature of the water bath, pour
the contents of both beakers into the 50 mL beaker.
d. Stir the contents of the 50 mL beaker with your Temperature Probe. After one minute,
record the temperature of the mixture.
e. Fill a clean, dry cuvette about ¾ full with the reaction mixture. Place the cuvette in the
Colorimeter. Close the lid on the Colorimeter.
f. Click to begin collecting ln absorbance data.
g. When the data collection is complete, carefully remove the cuvette from the Colorimeter.
Dispose of the contents of the beaker and cuvette as directed.
h. On the plot of ln absorbance vs. time for your latest trial, click the Linear Regression
button, . Record the rate constant, k, in your data table.
i. Close the Linear Regression box by clicking the X in the corner of the box.
11. Repeat Steps 9-10, using a water bath at ~20°C.

12. Repeat Steps 9-10, using a water bath at ~25°C.

13. Print a graph of ln absorbance vs. time, with all four trials displayed on the graph. Identify
each plot with its temperature value, by choosing Text Annotation from the Insert menu.

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DATA TABLE
Temperature Rate constant, k
Trial
(°C) (s-1)

DATA ANALYSIS
1. Plot a graph of your data above, using Temperature (°C) as the x-axis, and the rate constant,
k, as the y-axis.
a. Disconnect your Colorimeter and Temperature Probe from the interface.
b. Choose New from the File menu. An empty graph and table will be created in Logger Pro.
c. Double-click on the x-axis heading in the table, enter a name and unit, then enter the four
values for Temperature (°C) from your data table above.
d. Double-click on the y-axis heading in the table, enter a name and unit, then enter the four
values for the rate constant from your data table above.

2. In order to determine the activation energy, Ea, you will first need to plot the natural log of k
vs. the reciprocal of absolute temperature.
a. Choose New Calculated Column from the Data menu.
b. Create a column, ln rate constant, k.
c. Create a second column, reciprocal of absolute temperature, 1/(Temperature (°C) + 273).
d. On the displayed graph, plot ln rate constant on the y-axis and reciprocal of absolution
temperature on the x-axis by clicking on the respective axes labels. Autoscale the graph if
necessary.

3. Calculate the activation energy, Ea, for the reaction. To do this, first perform a linear fit on
the graph you created in Step 2 above. Use the slope, m, of the linear fit to calculate the
activation energy, Ea, in units of kJ/mol. Note: On a plot of ln k vs. 1/absolute temperature,
Ea = m × R.

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4. A well-known approximation in chemistry states that the rate of a reaction often doubles for
every 10°C increase in temperature. Use your data to test this rule. Calculate the ratio of the
rate constant at ~20°C to the rate constant at ~10°C. Then calculate the ratio of the rate
constant at ~25°C to the rate constant at ~15°C. How close were these values to a ratio of 2?
(Note: It is not necessarily equal to 2.00; this is just an approximate value, and depends on
the activation energy for the reaction.)

5. Using the rate constant and precise temperature value for the trial that was done at room
temperature (~20°C), as well as the Ea value you obtained in Step 3 above, calculate what the
rate constant would be at 40°C.

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Results: Data + Graphs 6
Ea Graph 1
Ea Calculation 2
Calculation of k ratios 2
Rate constants (10 and 40 oC) 2
Discussion 5
Conclusion 1
References 1_______
Total = 20 marks

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 The Rate and Order of
a Chemical Reaction

Experiment 6: Vernier # 25

A basic kinetic study of a chemical reaction often involves conducting the reaction at varying
concentrations of reactants. In this way, you can determine the order of the reaction in each
species, and determine a rate law expression. Once you select a reaction to examine, you must
decide how to follow the reaction by measuring some parameter that changes regularly as time
passes, such as temperature, pH, pressure, conductance, or absorbance of light.
In this experiment you will conduct the reaction between solutions of potassium iodide and iron
(III) chloride. The reaction equation is shown below, in ionic form.
2 I– (aq) + 2 Fe3+ (aq) → I2 (aq) + 2 Fe2+ (aq)
As this reaction proceeds, it undergoes a color change that can be precisely measured by a
Colorimeter (see Figure 1). By carefully varying the concentrations of the reactants, you will
determine the effect each reactant has on the rate of the reaction, and consequently the order of
the reaction. From this information, you will write a rate law expression for the reaction.

OBJECTIVES
In this experiment, you will
Conduct the reaction of KI and FeCl3 using various concentrations of reactants.
Determine the order of the reaction in KI and FeCl3.
Determine the rate law expression for the reaction.

Figure 1

MATERIALS
Vernier computer interface 0.020 M potassium iodide, KI, solution
computer 0.020 M iron (III) chloride, FeCl3, solution
Vernier Colorimeter distilled water
plastic cuvettes three 25 mL graduated cylinders
Advanced Chemistry with Vernier
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five plastic Beral pipets three 100 mL beakers

PROCEDURE
1. Obtain and wear goggles.

2. Connect a Colorimeter to Channel 1 of the Vernier computer interface. Connect the interface
to the computer with the proper cable.

3. Start the Logger Pro program on your computer. Open the file “25 Rate and Order” from the
Advanced Chemistry with Vernier folder.

4. Set up and calibrate the Colorimeter.

a. Prepare a blank by filling an empty cuvette ¾ full with distilled water. Place the blank in
the cuvette slot of the Colorimeter and close the lid.

b. If your Colorimeter has a CAL button, set the wavelength on the Colorimeter to 430 nm,
press the CAL button, and proceed directly to Step 5. If your Colorimeter does not have a
CAL button, continue with this step to calibrate your Colorimeter.
c. Choose Calibrate  CH1: Colorimeter from the Experiment menu, then click .
d. Turn the wavelength knob on the Colorimeter to the “0 % T” position.
e. Type “0” in the edit box.
f. When the displayed voltage reading for Reading 1 stabilizes, click .
g. Turn the knob of the Colorimeter to the Blue LED position (470 nm).
h. Type “100” in the edit box.
i. When the voltage reading for Reading 2 stabilizes, click , then click .
5. Obtain the materials you will need to conduct this experiment.
Three 25 mL graduated cylinders.
Approximately 100 mL of 0.020 M KI solution in a 100 mL beaker.
Approximately 100 mL of 0.020 M FeCl3 solution in a separate 100 mL beaker.
Approximately 60 mL of distilled water in a third 100 mL beaker.
6. During this experiment you will conduct 5 trials. This step describes the process for
conducting the trials using the Trial 1 volumes. When you repeat this process, use the correct
volume for each trial based on the table below.
Trial FeCl3 (mL) KI (mL) H2O (mL)
1 20.0 20.0 0.0
2 20.0 10.0 10.0
3 10.0 20.0 10.0
4 15.0 10.0 15.0
5 10.0 15.0 15.0

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 a. Measure 20.0 mL of FeCl3 solution into a 100 mL beaker.
b. Measure 20.0 mL of KI solution into a second 100 mL beaker.
c. Remove the cuvette from the Colorimeter and pour out the distilled water.
d. Add the 20.0 mL of FeCl3 solution to the beaker of KI solution. Swirl the beaker to mix.
e. Rinse the cuvette twice with ~1-mL amounts and then fill it ¾ full. Wipe the outside of
the cuvette with a tissue, place it in the Colorimeter, and close the lid.
7. Click to begin collecting absorbance data. Data will be gathered for 2 minutes.
Observe the progress of the reaction in the beaker.

8. When the data collection is complete, carefully remove the cuvette from the Colorimeter.
Dispose of the contents of the beaker and cuvette as directed. Rinse and clean the beakers
and the cuvette for the next trial.

9. Examine the graph of the first trial. Select a linear region of the graph that covers about 30-
40 seconds of the reaction. Click the Linear Regression button, . Record the slope, as the
initial rate of the Trial 1 reaction, in your data table and then close the Linear Regression
box.

10. Repeat Steps 6-9 to conduct Trials 2-5. Note: You will skip Step 6c in Trials 2-5.

DATA TABLE
–1
Trial [FeCl3] [KI] Initial rate (sec )

DATA ANALYSIS
1. Calculate the molar concentration of FeCl3 and KI for each reaction and record the values in
the table above. Provide one example to show how you completed the calculation.

2. What is the order of the reaction in FeCl3 and KI? Explain.

3. Write the rate law expression for the reaction.

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38
4. Is it possible to calculate the rate constant, k, from your data? If so, calculate the rate
constant. If not, explain why not.

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Data and Results 4
Calculations (Questions) 9 (3 + 3 + 3)
Discussion 5
Conclusion 1
References 1_ _
Total = 25 marks

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 The Base Hydrolysis
of Ethyl Acetate

Experiment 7: Vernier # 29

The reaction of ethyl acetate and hydroxide ions yields ethanol and acetate ions, as shown below.
CH3COOC2H5 (aq) + OH– (aq) → CH3CH2OH (aq) + CH3COO– (aq)
The progress of this reaction can be observed by monitoring the conductivity of the reaction
mixture. Although the reactants and products each contain an ion, the OH– ion has a higher ionic
mobility than the CH3COO– ion. This results in a net decrease in the conductivity of the reaction
mixture as the reaction proceeds.

Ethyl acetate is the major active ingredient in commercial acetone-free, nail-polish removers.
The molar concentration of CH3COOC2H5 in this product is 0.10 M. You can successfully use
one of these over-the-counter products in this experiment. The primary objective of this
experiment is to conduct a series of reactions from which you will determine the rate law
expression for the base hydrolysis of ethyl acetate.

OBJECTIVES
In this experiment, you will
Conduct the base hydrolysis of ethyl acetate under various conditions.
Calculate the rate law constant, k, for the reaction.
Determine the rate law expression for the reaction.

Figure 1

MATERIALS
Vernier computer interface 0.050 M sodium hydroxide, NaOH, solution
computer 0.10 M ethyl acetate, CH3COOC2H5, solution
Vernier Conductivity Probe two 50 mL graduated cylinders
thermometer or Temperature Probe room-temperature water bath
Advanced Chemistry with Vernier
40
 50 mL Erlenmeyer flask solid stopper to fit 50 mL Erlenmeyer flask
100 mL beaker distilled water

PROCEDURE
Part I React 0.050 M NaOH Solution with 0.10 M CH3COOC2H5 Solution at ~20°C
1. Obtain and wear goggles.

2. Prepare the reagents for temperature equilibration.

a. Set up a room-temperature water bath to immerse, but not cover, a 100 mL beaker. Make
sure that the water bath remains a constant temperature.
b. Measure out 30 mL of 0.050 M NaOH solution into a 100 mL beaker. Place the beaker in
the water bath.
c. Measure out 30 mL of 0.10 M ethyl acetate solution in a 50 mL Erlenmeyer flask.
Stopper the flask and place it in the water bath with the beaker.
3. Connect a Conductivity Probe to Channel 1 of the Vernier computer interface. Connect the
interface to the computer using the proper cable.

4. Set the toggle switch on the Conductivity Probe to the 0-20000 μS/cm range.

5. Start the Logger Pro program on your computer. Open the file “29 Ethyl Acetate” from the
Advanced Chemistry with Vernier folder.

6. Prepare to run the reaction and collect conductivity data.

a. Remove the beaker from the water bath and place the Conductivity Probe in the beaker.
Record the initial conductivity of the NaOH solution in your data table, but do not start
the data collection.
b. Pour the flask of CH3COOC2H5 solution into the beaker of NaOH solution. Stir the
mixture.
c. Place the beaker back into the water bath. Position the Conductivity Probe in the beaker
to collect precise readings.
7. Click to begin data collection. Data will be collected for five minutes. Gently hold the
beaker so that it stays immersed in the water bath.

8. When the data collection is complete, dispose of the contents of the beaker as directed. Rinse
and clean the beaker and flask for the second trial.

9. Examine the graph of your data. The graph will show a gradual, nonlinear, conductivity
decrease. Record the temperature of the water bath in your data table.

10. Click on the Linear Regression button, , to calculate the best-fit line equation. Record the
slope, in your data table, as the initial rate of the Trial 1 reaction and then close the Linear
Regression box by clicking the X in the corner of the box.

Part II React 0.050 M NaOH Solution with 0.050 M CH3COOC2H5 Solution at ~20°C
11. Measure out 30 mL of 0.050 M NaOH solution into the 100 mL beaker. Place the beaker in
the water bath.
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41
12. Measure out 15 mL of 0.10 M ethyl acetate solution and 15 mL of distilled water in the
50 mL Erlenmeyer flask. Stopper the flask and place it in the water bath with the beaker.

13. Repeat Steps 6-10 to complete the second trial.

Part III React 0.025 M NaOH Solution with 0.10 M CH3COOC2H5 Solution at ~20°C
14. Measure out 15 mL of 0.050 M NaOH solution and 15 mL of distilled water into the 100 mL
beaker. Place the beaker in the water bath.

15. Measure out 30 mL of 0.10 M ethyl acetate solution in the 50 mL Erlenmeyer flask. Stopper
the flask and place it in the water bath with the beaker.

16. Repeat Steps 6-10 to complete the third trial.

DATA TABLE
Initial conductivity
Temperature Initial rate
Trial Reactants of NaOH solution
(°C) (μS/(cm•s))
(μS/cm)

30 mL 0.050 M NaOH +
1
30 mL 0.10 M CH3COOC2H5
30 mL 0.050 NaOH +
2
30 mL 0.050 M CH3COOC2H5
30 mL 0.025 M NaOH +
3
30 mL 0.10 M CH3COOC2H5

DATA ANALYSIS

1. What is the order of the reaction in sodium hydroxide and ethyl acetate? Explain how you
determined order for each reactant.

2. Write the rate law expression for the reaction.

3. Convert conductivity to molar concentration by using the initial conductivity of the NaOH
solution as a conversion factor. Convert each initial rate into the units: moles/L-sec. For
example, if the initial conductivity of the NaOH solution was 14000 μS/cm and initial rate
was 10.5 μS /cm•sec, you would convert the rate to moles/L•sec by completing the following

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42
 calculation: Rate = 10.5 μS/cm•sec [(0.05 mol/L)/(14000 μS/cm)] = 3.75 10–5 mol/L•sec.
Use these new values to calculate the rate constant, k.

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Data and Results 6
Calculations (Questions) 7 (4 + 1 + 2)
Discussion 5
Conclusion 1
References 1_ _
Total = 25 marks

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 The Determination of
an Equilibrium Constant

Experiment 8: Vernier # 10

Chemical reactions occur to reach a state of equilibrium. The equilibrium state can be
characterized by quantitatively defining its equilibrium constant, Keq. In this experiment, you will
determine the value of Keq for the reaction between iron (III) ions and thiocyanate ions, SCN–.
Fe3+ (aq) + SCN– (aq) → FeSCN2+ (aq)
The equilibrium constant, Keq, is defined by the equation shown below.
2
[ FeSCN ]
K eq 3
[ Fe ][SCN ]
To find the value of Keq, which depends only upon temperature, it is necessary to determine the
molar concentration of each of the three species in solution at equilibrium. You will use a
colorimeter to help you measure the concentrations (see Figure 1). The amount of light absorbed
by a colored solution is proportional to its concentration. The red FeSCN2+ solution absorbs blue
light, and it will be analyzed at 470 nm (blue light).

Figure 1

In order to successfully evaluate this equilibrium system, it is necessary to conduct three separate
tests. First, you will prepare a series of standard solutions of FeSCN2+ from solutions of varying
concentrations of SCN– and constant concentrations of H+ and Fe3+ that are in stoichiometric
excess. The excess of H+ ions will ensure that Fe3+ engages in no side reactions (to form FeOH2+,
for example). The excess of Fe3+ ions will make the SCN– ions the limiting reagent, thus all of
the SCN– used will form FeSCN2+ ions. The FeSCN2+ complex forms slowly, taking at least one
minute for the color to develop. It is best to take absorbance readings after a specific amount of
time has elapsed, between two and four minutes after preparing the equilibrium mixture. Do not
wait much longer than four minutes to take readings, however, because the mixture is light
sensitive and the FeSCN2+ ions will slowly decompose.

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In Part II of the experiment, you will analyze a solution of unknown [SCN–] by using the same
procedure that you followed in Part I. In this manner, you will determine the molar concentration
of the SCN– solution.

Third, you will prepare a new series of solutions that have varied concentrations of the Fe3+ ions
and the SCN– ions, with a constant concentration of H+ ions. You will use the results of this test
to accurately evaluate the equilibrium concentrations of each species.

OBJECTIVES
In this experiment, you will
Prepare and test standard solutions of FeSCN2+ in equilibrium.
Test solutions of SCN– of unknown molar concentration.
Determine the molar concentrations of the ions present in an equilibrium system.
Determine the value of the equilibrium constant, Keq, for the reaction.

MATERIALS

Vernier computer interface 0.200 M iron (III) nitrate, Fe(NO3)3, solution

computer in 1.0 M HNO3
Vernier Colorimeter 0.0020 M iron (III) nitrate, Fe(NO3)3, solution
Temperature Probe (optional) in 1.0 M HNO3
plastic cuvette 0.0020 M thiocyanate, SCN–, solution in
four 10.0 mL pipettes 0.10 M HNO3
pipet pump or bulb potassium thiocyanate, KSCN solution of
six 20 × 150 mm test tubes unknown concentration in 0.10 M HNO3
50 mL volumetric flask test tube rack
eight 100 mL beakers distilled water
plastic Beral pipets tissue

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45
PRE-LAB EXERCISE
For the solutions that you will prepare in Step 2 of Part I below, calculate the [FeSCN2+].
Presume that all of the SCN– ions react. In Part I of the experiment, mol of SCN– = mol of
FeSCN2+. Thus, the calculation of [FeSCN2+] is: mol FeSCN2+ ÷ L of total solution. Record
these values in the table below.

2+
Beaker number [FeSCN ]

1 0.00 M

PROCEDURE
Part I Prepare and Test Standard Solutions
1. Obtain and wear goggles.

2. Label five 100 mL beakers 1-5. Obtain small volumes of 0.200 M Fe(NO3)3,
0.0020 M SCN–, and distilled water. CAUTION: Fe(NO3)3 solutions in this experiment are
prepared in 1.0 M HNO3 and should be handled with care. Prepare four solutions according
to the chart below. Use a 10.0 mL pipet and a pipet pump or bulb to transfer each solution to
a 50 mL volumetric flask. Mix each solution thoroughly. Measure and record the temperature
of one of the above solutions to use as the temperature for the equilibrium constant, Keq.
–
Beaker 0.200 M Fe(NO3)3 0.0020 M SCN H2O
number (mL) (mL) (mL)
1 5.0 0.0 45.0
2 5.0 2.0 43.0
3 5.0 3.0 42.0
4 5.0 4.0 41.0
5 5.0 5.0 40.0

3. Connect a Colorimeter to Channel 1 of the Vernier computer interface. Connect the interface
to the computer with the proper cable.

4. Start the Logger Pro program on your computer. Open the file “10 Equilibrium” from the
Advanced Chemistry with Vernier folder.

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46
5. Calibrate the Colorimeter.
a. Prepare a blank by filling an empty cuvette ¾ full with distilled water. Place the blank in
the cuvette slot of the Colorimeter and close the lid.
b. If your Colorimeter has a CAL button, set the wavelength on the Colorimeter to 470 nm,
press the CAL button, and proceed directly to Step 6. If your Colorimeter does not have a
CAL button, continue with this step to calibrate your Colorimeter.
c. Choose Calibrate  CH1: Colorimeter from the Experiment menu, then click .
d. Turn the wavelength knob on the Colorimeter to the “0% T” position.
e. Type “0” in the edit box.
f. When the displayed voltage reading for Reading 1 stabilizes, click .
g. Turn the knob of the Colorimeter to the Blue LED position (470 nm).
h. Type “100” in the edit box.
i. When the voltage reading for Reading 2 stabilizes, click , then click .
6. You are now ready to collect absorbance data for the standard solutions. Click to
begin data collection. Note: Take readings within 4 minutes of preparing the mixtures.
a. Empty the water from the cuvette. Using the solution in Beaker 1, rinse the cuvette twice
with ~1 mL amounts and then fill it ¾ full. Wipe the outside with a tissue, place it in the
Colorimeter, and close the lid. Wait for the absorbance value displayed in the Meter
window to stabilize. Click , type the concentration of FeSCN2+ (from your pre-lab
calculations) in the edit box, and press the ENTER key.
b. Discard the cuvette contents as directed. Rinse and fill the cuvette with the solution in
Beaker 2. Follow the procedure in Part a of this step to measure the absorbance, and enter
the concentration of this solution.
c. Repeat Part b of this step to measure the absorbance of the solutions in Beakers 3, 4,
and 5.
d. Click when you have finished collecting data. Click the Examine button, , and
record the absorbance values for each data pair.
e. Click the Linear Fit button, . A best-fit linear regression line will be shown for your
five data points. This line should pass near or through the data points and the origin of the
graph. (Note: Another option is to choose Curve Fit from the Analyze menu, and then
select Proportional. The Proportional fit has a y-intercept value equal to 0; therefore, this
regression line will always pass through the origin of the graph).
Leave the graph and best fit line displayed and proceed to Step 8.
–
Part II Test an Unknown Solution of SCN
8. Obtain about 10 mL of the unknown SCN– solution. Use a pipet to measure out 5.0 mL of the
unknown into a clean and dry 100 mL beaker. Add precisely 5.0 mL of 0.200 M Fe(NO3)3
and 40.0 mL of distilled water to the beaker. Stir the mixture thoroughly.

9. Using the solution in the beaker, rinse a cuvette twice with ~1 mL amounts and then fill
it ¾ full. Wipe the outside with a tissue, place it in the Colorimeter, and close the lid.
Watch the absorbance readings in the Meter window. When the readings stabilize, record the
absorbance value for your unknown in your data table. Remove and clean the cuvette.

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47
 10. Determine the concentration of the unknown SCN– solution.
a. With the linear-regression curve still displayed on your graph, choose Interpolate from
the Analyze menu.
b. A vertical line with a cursor now appears on the graph. The cursor’s concentration and
absorbance coordinates are displayed in the floating box.
c. Move the cursor along the regression line until the absorbance value is approximately the
same as the absorbance value you recorded in Step 9. The corresponding concentration
value is the concentration of the unknown solution, in mol/L. Record this value in your
data table.

Part III Prepare and Test Equilibrium Systems

11. Prepare five test tubes of solutions, according to the chart below. Follow the necessary steps
from Part I to test the absorbance values of each mixture. Record the test results in your data
table. Note: You are using 0.0020 M Fe(NO3)3 in this test.
–
Test tube 0.0020 M Fe(NO3)3 0.0020 M SCN H2O
number (mL) (mL) (mL)
1 3.00 0.00 7.00
2 3.00 2.00 5.00
3 3.00 3.00 4.00
4 3.00 4.00 3.00
5 3.00 5.00 2.00

12. To get good data for the calculation of Keq, you must determine the net absorbance of the
solutions in Test Tubes 2-5. To do this, subtract the absorbance reading for Test Tube 1 from
the absorbance readings of Test Tubes 2-5, and record these values as net absorbance in your
data table.

DATA TABLE

Parts I and II
Beaker Absorbance

Unknown, Part II

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48
Best-fit line equation for the Part I standard solutions:

Part III
Test tube number Absorbance Net absorbance

DATA ANALYSIS
1. (Part II) Use the calibration equation from Item 1 and the absorbance reading for your
unknown solution to determine [SCN–].

2. (Part II) Compare your experimental [SCN–], of your unknown, with the actual [SCN–].
Suggest reasons for the disparity.

3. (Part III) Use the net absorbance values, along with the best fit line equation of the standard
solutions in Part I to determine the [FeSCN2+] at equilibrium for each of the mixtures that
you prepared in Part III. Complete the table below and give an example of your calculations.

Test tube number 2 3 4 5

2+
[FeSCN ]

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4. (Part III) Calculate the equilibrium concentrations for Fe3+ and SCN– for the mixtures in Test
tubes 2-5 in Part III. Complete the table below and give an example of your calculations.

Test tube number 2 3 4 5

3+
[Fe ]

–
[SCN ]

5. Calculate the value of Keq for the reaction. Explain how you used the data to calculate Keq.

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Prelab Exercise 2
Data and Results 4
Data Analysis (Questions) 8 (1 + 1 + 2 + 2 + 2)
Discussion 4
Conclusion 1
References 1__
Total = 25 marks

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 Determining Ka by the
Half-Titration of a Weak Acid

Experiment 9: Vernier # 24

A common analysis of a weak acid or a weak base is to conduct a titration with a base or acid of
known molar concentration to help determine the equilibrium constant, Ka, for the weak acid or
weak base. If this titration is conducted very carefully and very precisely, the results can lead to a
valid approximation of an equilibrium constant. In this experiment, however, you will use a
different technique to determine the Ka for a weak acid, acetic acid.
Your primary goal in this experiment is to calculate the Ka of acetic acid. The data that you will
use to complete your calculations will come from the reaction of acetic acid with a solution of
NaOH. Recall from your work with weak acid-strong base titrations that the point at which a
reaction is half-titrated can be used to determine the pKa of the weak acid. In this experiment, the
half-titration point will exist when you have added half as many moles of HC2H3O2 as moles of
NaOH . Thus, OH– will have reacted with half of the HC2H3O2, leaving the solution with equal
moles of HC2H3O2 and C2H3O2 –. At this point, according to the Henderson-Hasselbalch
equation,
[C 2 H 3 O 2 ]
pH pK a log
[ HC 2 H 3 O 2 ]

if there are equal moles of HC2H3O2 and C2H3O2 – at the half-titration point, then pKa is equal to
the pH value of the solution.

In this experiment, you may find it surprising that you do not need to keep close track of the
volume of NaOH titrant added, as you would in most titrations. It is also unusual to conduct a
titration without plotting or analyzing a conventional titration curve. This is the nature of a half-
titration; it is only important to know when equal amounts of OH– and HC2H3O2 have been
added.

OBJECTIVES
In this experiment, you will
Conduct a reaction between solutions of a weak acid and sodium hydroxide.
Determine the half-titration point of an acid-base reaction.
Calculate the pKa and the Ka for the weak acid.

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 Figure 1

MATERIALS
Vernier computer interface 1.00 M sodium hydroxide, NaOH, solution
computer 1.00 M acetic acid, HC2H3O2, solution
Vernier pH Sensor phenolphthalein indicator solution
50 mL buret distilled water
buret clamp magnetic stirrer and stirring bar
250 mL beaker plastic Beral pipets
two ring stands utility clamp

PROCEDURE
1. Obtain and wear goggles.

2. Use a buret clamp to connect a 50 mL buret to a ring stand. Rinse and fill the buret with
1.00 M acetic acid solution. Handle the acetic acid with care. It can cause painful burns if it
comes into contact with the skin.

3. Transfer precisely 25.0 mL of the acetic acid solution to a 250 mL beaker.

3. Use a plastic Beral pipet to remove a small volume of the acetic acid from the 250 mL
beaker. Draw enough acetic acid into the pipet so that the bulb is about ¼ full. Carefully set
aside the pipet of acid, to be used later.

4. Add 1-2 drops of phenolphthalein indicator solution to the beaker of acetic acid.

5. Connect a pH Sensor to Channel 1 of the Vernier computer interface. Connect the interface
to the computer using the proper cable.

6. Start the Logger Pro program on your computer. Open the file “24 Half-Titration” from the
Advanced Chemistry with Vernier folder.

7. Obtain about 50 mL of 1.00 M NaOH solution. CAUTION: Sodium hydroxide solution is

caustic. Avoid spilling it on your skin or clothing.

8. Begin the half-titration.

a) Place the beaker of acetic acid on a magnetic stirrer and add a stirring bar.
Advanced Chemistry with Vernier
52
 b) Set up a ring stand and clamp to hold the pH Sensor in place (see Figure 1).
Position the pH Sensor in the beaker so that the tip of the probe is completely
immersed.
c) Gently stir the acetic acid solution.
d) Click to begin monitoring pH. A meter and table will be displayed.
e) Use a new plastic Beral pipet to slowly add the 1.00 M NaOH solution, in ~1 mL
increments, to the beaker of acetic acid solution (see Figure 1).
f) Click to record pH readings, as you feel necessary, to help you follow the
reaction.
9. Conduct the titration carefully. As the reaction approaches the equivalence point, at about
pH 6, add the NaOH solution drop by drop. When you reach the equivalence point, the pH
will increase rapidly and the indicator will change color. If necessary, add another drop of
NaOH, so that the reaction is slightly past the equivalence point. Remember that the pH will
not increase rapidly beyond the equivalence point (pH ~10).

10. Add all of the acetic acid from the Beral pipet, which you removed in Step 3, to the beaker of
reaction mixture. Check the pH readings and observe the indicator color. The mixture should
be slightly acidic once again.

11. Carefully add NaOH, drop by drop, to the beaker of reaction mixture, until you reach the
equivalence point as precisely as possible. A very slight pink color of the phenolphthalein
indicator is visible. This is your half-titrated solution, because you have neutralized precisely
25.0 mL of the original 50.0 mL of acetic acid that you measured out into the buret.

12. Transfer the remaining 25.0 mL of acetic acid from the buret to the 250 mL beaker of
reaction mixture. Stir the solution in the beaker thoroughly. When the reading is stable, click
, then click . Read and record the final pH of the solution in the beaker.

13. When you have finished the testing, dispose of the reaction mixture as directed. Rinse the pH
Sensor with distilled water in preparation for a second trial. Repeat the necessary steps to test
a new sample of the acetic acid solution.

DATA TABLE
Titration Results Trial 1 Trial 2

Equivalence point pH

pH of half-titrated solution

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DATA ANALYSIS

1. Calculate the pKa and Ka using the results of your testing.

2. Find the accepted values for the pKa and Ka of acetic acid. How well do the accepted values
compare with your calculated values? Explain.

3. Explain why the pH at the half-titration point is equal to the pKa in your experiment.

4. Explain how this test could be done using only an indicator solution and no electronic means
of measuring pH.

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54
 THE ADSORPTION OF ACETIC ACID FROM
AQUEUOS SOLUTION BY CHARCOAL
Experiment 10

AIM
To investigate the adsorption of acetic acid on a given amount of charcoal.

THEORY
Adsorption is the withdrawal of a substance from a bulk phase (gaseous or solution) and its
accumulation at an interface. The surface concentration of the solute (moles of solute per unit
area of adsorbent surface or per gram of adsorbent) attained at equilibrium at a given temperature
is generally found to vary with the concentration of the solute in the bulk phase as shown below.

This is the behavior predicated by the Langmuir adsorption isotherm, which may be derived
theoretically assuming that
(a) the surface is uniform in its adsorptive properties,
(b) the presence of an adsorbed molecule on a surface site does not significantly alter the
probability of occupation of a neighboring site – i.e. the interaction between neighboring
adsorbed molecules is negligible.
(c) adsorption occurs to give an adsorbed layer with a thickness of only one molecule
( mono-molecular layer).
(d) the adsorbed molecules do not dissociate on the surface.

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According to the Langmuir isotherm, ø the fraction of the surface covered, when the bulk
concentration is C, is
Ø = kc/ (1+kc) = X/Xmax
(1)
where, for adsorption of acetic acid by charcoal,
c = concentration of acetic acid solution, in mol dm-3, which is in equilibrium with acetic
acid adsorbed on the charcoal.
X = number of moles of acetic acid adsorbed by one gram of charcoal when the solution
in contract with it has the equilibrium concentration; k is an empirical constant.

This can be rearranged into the form

c/x = a + bc (2)
where a = 1/kXmax and b= 1/ Xmax
Xmax is the maximum number of the moles of acetic acid adsorbed as a mono molecular layer per
gram of charcoal.

The area occupied by each molecule of acetic on any adsorbing surface is known to be 21 × 10-20
m2. This information, together with the experimentally determined constant b of the Langmuir
isotherm, permits an estimation of the area of active surface per gram, (the specified area, S) for
the sample of the charcoal used.

S = Xmax .L.21× 10-20 m2

Where < is the Avogadro constant (6.023 × 10-23 mol-1).
By equation (2) the constant b required for this calculation is equal to the slope of a plot of c/X
versus c.

APPARATUS & CHEMICALS

Four clean and dry 250 cm3 conical flasks with glass or rubber stoppers; fine porosity filter
paper; stirring rod; burette; several 100 cm3 titration flasks; pipettes (5 cm3, 10cm3, and 25 cm3).

EXPERIMENTAL
Label four clean and dried glass- stoppered bottles. To the first three add about 0.5 g of the
charcoal with a spatula then weigh the bottle and charcoal. For the last bottle add about 1 g of
charcoal. All weighings should be done to ± mg.

[CAUTION--- the charcoal is very finely divided and easily becomes airborne. Handle carefully
with a spatula during the weighing operations and carry out transfer well away from the balance.]

Pipette into each bottle the amount of distilled water shown in the table and finally the 1 mol dm-
3
acetic acid (laboratory stock solution). Stopper the bottles and shake well at intervals over a
period of not less than half an hour (using a mechanical shaker if available). Record the
temperature.

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56
Bottle Wt. of Volume of Vol. of nominally 1 mol Suitable volumes
charcoal/g water/cm3 dm-3 acetic acid/cm3 of filtrate/ cm3
1 1 100 5 25
2 1 50 5 10
3 1 50 10 5
4 2 25 20 5

Equilibrate the acetic acid solutions and charcoal for about 30 minutes. Use this time to prepare
and label six dry conical flasks each with a filter funnel and a dry Whatman No. 42 filter paper.
Dilute 50 cm3 of 1 mol dm-3 NaOH to 1 dm3, using distilled water and calculate the
concentration from the actual molarity marked on the stock bottle.

The six solutions were filtered, rejecting the first 10 cm3 of filtrate, the concentration of which
may be altered by adsorption on the filter paper. Then collect the reminder in the labeled conical
flasks and withdraw by pipette the volumes indicated in the above table for duplicate titrations
with the 0.05 mol dm-3 NaOH.

QUESTIONS
(i) Calculate for each system:
c = concentration of acetic acid, in mol dm-3, in the solution at equilibrium) and
X = number of moles of acetic acid adsorbed per gram of charcoal).
X is calculated from the difference between the numbers of moles of acetic acid present
in solution after adsorption has occurred.
(ii) Plot X against c and note that X tends to a limit as c increases and that the curve
must pass through the origin.

(iii) Plot c/X versus c and evaluate b of equation (2) from the slope. Using the given value for
the area covered by each molecule of acetic acid calculate the specific area of the
charcoal.

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 Enthalpy of Vapourization of Water From
Vapour Pressure Measurements
Experiment 11

Objective
To determine the enthalpy of vapourization of water from the measurement of vapour pressure at
various temperatures.

Introduction
The Clausius-Clapeyron equation gives a relationship between the vapour pressure of a pure
liquid and the temperature of that liquid. The relationship can be written simply as:

ln p = -Hvap / RT + constant

where (H is the enthalpy of vapourization of the liquid. The equation is derived from
consideration of equal Gibbs free energy for liquid and vapour in equilibrium, and several
assumptions are involved. The main ones are: (i) the volume of vapour is assumed to be much
greater than that of the liquid vapourized, and (ii) it is assumed that the vapour behaves like an
ideal gas.

In this experiment the sample of air is trapped over water in an inverted measuring cylinder in a
beaker. When the temperature of the apparatus is changed, the number of moles of water vapour
in the gas phase will vary according according to the Clausius-Clapeyron equation, while that of
air will remain constant. The number of moles of air in the mixture can be found by reducing the
temperature of the whole apparatus to about 5 oC, where the vapour pressure of water is so small
that the entire volume of gas can be assumed to be air.
The enthalpy of vapourization can then be calculated from a plot of ln p versus l/T.

Apparatus
10-cm3 measuring cylinder, thermometer (preferably one reading to + 0.1 oC), a tall beaker
(preferably a 1L beaker), bunsen burner, Ice and Ice-bath.

Procedure

1. 1. Fill a 10-cm3 graduated measuring cylinder about 80 % full with distilled water. Cover the
top with a finger and quickly invert and lower the cylinder into a tall beaker that has been filled
with tap water. An air sample of 3 to 4 cm3 should be trapped within the cylinder. Head-up a
table with time, volume and temperature and record this volume and the temperature.

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2. Add more water if necessary to the beaker to ensure that whole cylinder is surrounded by
water. Then SLOWLY heat with a Bunsen burner to about 80 oC. During heating record the
time, volume and temperature at every 5 oC.

3. When the volume of the trapped air expands beyond the scale on the cylinder, remove the
burner and allow the water to cool slowly. When the gas begins to contract and the volume can
again be read, read and record the volume to the closest 0.1 cm3 and the temperature of the water
to the nearest 0.1 oC. Stir the water bath frequently to avoid thermal gradients. As the water
cools, make additional measurements of temperature at approximately 0.2 cm3 intervals down to
about 50 oC .

4. After the temperature has reached 50 oC, cool the water rapidly to less than 5 oC by adding
ice. Record the gas volume and the water temperature. Record the gas volume and the water
temperature again at 5 and 10 minutes after reaching about 5 oC. By then an equilibrium has
been reached again.

5. Obtain a reading of the atmospheric pressure (in atm).

Calculations
1. Correct all volume readings by subtracting 0.2 cm3 to compensate for the inverted
meniscus. Using the measured values for volume and temperature from step 4 and the
atmospheric pressure, calculate the number of moles, nair , of trapped air. Assume that
the vapour pressure of water is negligible compared to the atmospheric pressure at the
low temperature.

2. For each temperature between 80 and 50 oC, calculate the partial pressure of air in the gas
mixture. (NB: Use only the Cooling data from 80 – 50 oC in your calculations)

Pair = nairRT
V

3. Calculate the vapour pressure of water at each temperature:

PH2O = Patm - Pair

4. Plot ln PH2O versus l/T and draw the best straight line. Determine Hvap from the slope
and PH2O at 20 and 25 oC. Determine the standard deviation of Hvap by the “box
method”. Or otherwise use the excel program to evaluate the value of Hvap and its
associated error.

Discussion
Provide a comprehensive discussion of the main sources of errors in this experiment. Compare
Hvap and PH2O at 20 oC with literature values.
Are there any other assumptions other than those already mentioned which are worth
mentioning? Include these assumptions and explanations in your discussion.
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 Determining the Enthalpy
of Some Chemical Reactions

Experiment 12: Vernier # 13

All chemical reactions involve an exchange of heat energy; therefore, it is tempting to plan to
follow a reaction by measuring the enthalpy change (∆H). However, it is often not possible to
directly measure the heat energy change of the reactants and products (the system). We can
measure the heat change that occurs in the surroundings by monitoring temperature changes. If
we conduct a reaction between two substances in aqueous solution, then the enthalpy of the
reaction can be indirectly calculated with the following equation.

q = Cp m ∆T

The term q represents the heat energy that is gained or lost. Cp is the specific heat of water, m is
the mass of water, and ∆T is the temperature change of the reaction mixture. The specific heat
and mass of water are used because water will either gain or lose heat energy in a reaction that
occurs in aqueous solution. Furthermore, according to a principle known as Hess’s law, the
enthalpy changes of a series of reactions can be combined to calculate the enthalpy change of a
reaction that is the sum of the components of the series.

In this experiment, you will measure the temperature change of two reactions, and use Hess’s
law to determine the enthalpy change, ΔH of a third reaction. You will use a Styrofoam cup
nested in a beaker as a calorimeter, as shown in Figure 1. For purposes of this experiment, you
may assume that the heat loss to the calorimeter and the surrounding air is negligible.

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OBJECTIVES
In this experiment, you will
Use Hess’s law to determine the enthalpy change of the reaction between aqueous
ammonia and aqueous hydrochloric acid.
Compare your calculated enthalpy change with the experimental results.

Figure 1

MATERIALS
Vernier computer interface 2.0 M hydrochloric acid, HCl, solution
computer 2.0 M sodium hydroxide, NaOH, solution
Temperature Probe 2.0 M ammonium chloride, NH4Cl, solution
Styrofoam cup 2.0 M ammonium hydroxide, NH4OH, solution
250 mL beaker ring stand
50 mL or 100 mL graduated cylinders utility clamp
glass stirring rod fume hood

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PRE-LAB EXERCISE
You will conduct the following three reactions in this experiment. In the space provided below,
write the balanced net ionic reaction equations from the descriptions. Use the table of
thermodynamic data in your text (or another approved resource) to calculate the molar enthalpy
of the reactions.

Reaction 1: An aqueous solution of sodium hydroxide reacts with an aqueous solution of

hydrochloric acid, yielding water.

Reaction 2: An aqueous solution of sodium hydroxide reacts with an aqueous solution of

ammonium chloride, yielding aqueous ammonia, NH3, and water.

Reaction 3: An aqueous solution of hydrochloric acid reacts with aqueous ammonia, NH3,
yielding aqueous ammonium chloride.

Reaction Balanced reaction equation ΔH (kJ/mol)

PROCEDURE
1. Obtain and wear goggles. It is best to conduct this experiment in a fume hood, or in a
well-ventilated room.

2. Connect a Temperature Probe to Channel 1 of the Vernier computer interface. Connect the
interface to the computer with the proper cable. Use a utility clamp to suspend the
Temperature Probe from a ring stand, as shown in Figure 1.

3. Start the Logger Pro program on your computer. Open the file “13 Enthalpy” from the
Advanced Chemistry with Vernier folder.

Part I Conduct the Reaction Between Solutions of NaOH and HCl

4. Nest a Styrofoam cup in a beaker (see Figure 1). Measure 50.0 mL of 2.0 M HCl solution
into the cup. Lower the tip of the Temperature Probe into the HCl solution. CAUTION:
Handle the hydrochloric acid with care. It can cause painful burns if it comes in contact with
the skin.

5. Measure out 50.0 mL of NaOH solution, but do not add it to the HCl solution yet.
CAUTION: Handle the sodium hydroxide solution with care.

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 6. Conduct the reaction.
a. Click to begin the data collection and obtain the initial temperature of the HCl
solution.
b. After three or four readings have been recorded at the same temperature, add the 50.0 mL
of NaOH solution to the Styrofoam cup all at once. Stir the mixture throughout the
reaction.
c. Data collection will end after three minutes. If the temperature readings are no longer
changing, you may terminate the trial early by clicking .
d. Click the Statistics button, . The minimum and maximum temperatures are listed in the
statistics box on the graph. If the lowest temperature is not a suitable initial temperature,
examine the graph and determine the initial temperature.
e. Record the initial and maximum temperatures in your data table.
7. Rinse and dry the Temperature Probe, Styrofoam cup, and the stirring rod. Dispose of the
solution as directed.

Part II Conduct the Reaction Between Solutions of NaOH and NH 4Cl

8. Measure out 50.0 mL of 2.0 M NaOH solution into a nested Styrofoam cup (see Figure 1).
Lower the tip of the Temperature Probe into the cup of NaOH solution.

9. Measure out 50.0 mL of 2.0 M NH4Cl solution, but do not add it to the NaOH solution yet.

10. Conduct the reaction.

a. Click to begin the data collection.
b. After three or four readings have been recorded at the same temperature, add the 50.0 mL
of NH4Cl solution to the Styrofoam cup all at once. Stir the mixture throughout the
reaction.
c. Data collection will end after three minutes. If the temperature readings are no longer
changing, you may terminate the trial early by clicking .
d. Examine the graph as before to determine and record the initial and maximum
temperatures of the reaction.
11. Rinse and dry the Temperature Probe, Styrofoam cup, and the stirring rod. Dispose of the
solution as directed.

Part III Conduct the Reaction Between Solutions of HCl and NH 3

12. Measure out 50.0 mL of 2.0 M HCl solution into a nested Styrofoam cup (see Figure 1).
Lower the tip of the Temperature Probe into the cup of HCl solution.

13. Measure out 50.0 mL of 2.0 M NH3 solution, but do not add it to the HCl solution yet.

14. Conduct this reaction in a fume hood or in a well-ventilated area. Repeat Step 10 to conduct
the reaction and collect temperature data.

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DATA TABLE
Reaction 1 Reaction 2 Reaction 3

Maximum temperature (°C)

Initial temperature (°C)

Temperature change (∆T)

DATA ANALYSIS
1. Calculate the amount of heat energy, q, produced in each reaction. Use 1.03 g/mL for the
density of all solutions. Use the specific heat of water, 4.18 J/(g•°C), for all solutions.

2. Calculate the enthalpy change, ∆H, for each reaction in terms of kJ/mol of each reactant.

3. Use your answers from 2 above and Hess’s law to determine the experimental molar enthalpy
for Reaction 3.

4. Use Hess’s law, and the accepted values of ∆H in the Pre-Lab Exercise to calculate the ∆H
for Reaction 3. How does the accepted value compare to your experimental value?

5. Does this experimental process support Hess’s law? Suggest ways of improving your
results.

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Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Prelab Exercise 3
Data and Results 3
Calculations (Questions) 8 (2 + 2 + 2 + 2)
Discussion 4
Conclusion 1
References 1__
Total = 25 marks

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 The Enthalpy of Neutralization
of Phosphoric Acid

Experiment 13: Vernier # 26

As you have seen in previous experiments, a great deal can be learned by conducting an acid-
base reaction as a titration. In addition, acid-base reactions can be observed and measured
thermodynamically. In this case, the reaction is carried out in a calorimeter. If the temperature
of the reaction is measured precisely, the enthalpy of neutralization of an acid by a base (or vice
versa) can be determined. In this experiment, you will react phosphoric acid with sodium
hydroxide.
You will use a Styrofoam cup nested in a beaker as a calorimeter, as shown in Figure 1. For
purposes of this experiment, you may assume that the heat loss to the calorimeter and the
surrounding air is negligible. Phosphoric acid will be the limiting reactant in this experiment,
and you will accordingly be determining the enthalpy, ΔH, of neutralization of the acid.
Selecting a limiting reactant helps ensure that the temperature measurements and subsequent
calculations are as precise as possible.

OBJECTIVES
In this experiment, you will:
Measure the temperature change of the reaction between solutions of sodium hydroxide
and phosphoric acid.
Calculate the enthalpy, ΔH, of neutralization of phosphoric acid.
Compare your calculated enthalpy of neutralization with the accepted value.

Figure 1

MATERIALS
Vernier computer interface 0.60 M phosphoric acid, H3PO4, solution
computer 1.85 M sodium hydroxide, NaOH, solution
Temperature Probe two 50 mL graduated cylinders
Advanced Chemistry with Vernier
66
Styrofoam cup ring stand
two 250 mL beakers utility clamp
glass stirring rod

PROCEDURE
1. Obtain and wear goggles. It is best to conduct this experiment in a well-ventilated room.

2. Connect a Temperature Probe to Channel 1 of the Vernier computer interface. Connect the
interface to the computer with the proper cable.

3. Start the Logger Pro program on your computer. Open the file “26 Phosphoric Acid” from
the Advanced Chemistry with Vernier folder.

4. Nest a Styrofoam cup in a 250 mL beaker as shown in Figure 1. Measure out 50.0 mL of
0.60 M H3PO4 solution into the foam cup. CAUTION: Handle the phosphoric acid with
care. It can cause painful burns if it comes in contact with the skin.

5. Use a utility clamp to suspend the Temperature Probe from a ring stand (see Figure 1).
Lower the Temperature Probe into the phosphoric acid solution.

6. Measure out 50.0 mL of 1.85 M NaOH solution and transfer it to a 250 mL beaker.
CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin or clothing.

7. Conduct the experiment.

a. Click to begin the data collection and obtain the initial temperature of the H3PO4
solution.
b. After you have recorded three or four readings at the same temperature, add the 50.0
mL of NaOH solution to the Styrofoam cup all at once. Use a glass stirring rod to
stir the reaction mixture gently and thoroughly.
c. Data will be collected for 10 minutes. You may terminate the trial early by clicking
, if the temperature readings are no longer changing.
d. Click the Statistics button, . The minimum and maximum temperatures are listed in
the statistics box on the graph. If the minimum temperature is not a suitable initial
temperature, examine the graph and determine the initial temperature.
e. Record the initial and maximum temperatures, in your data table, for Trial 1.
f. Close the Statistics box by clicking the X in the corner of the box.
8. Rinse and dry the Temperature Probe, Styrofoam cup, and stirring rod. Dispose of the
solution as directed.

9. Repeat Steps 4-8 to conduct a second trial. If directed, conduct a third trial. Print a copy of
the graph of the second trial to include with your data and analysis.

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67
DATA TABLE

Trial 1 Trial 2 Trial 3

Maximum temperature (°C)
Initial temperature (°C)
Temperature change (∆T)

DATA ANALYSIS
1. Write the balanced equation for the reaction of phosphoric acid and sodium hydroxide.

2. Use the equation below to calculate the amount of heat energy, q, produced in the reaction. In
determining the mass, m, of the solution use 1.11 g/mL for the density. Use 4.18 J/(g•°C) as
the specific heat, Cp, of the solution. q = Cp m ∆T

3. Use the heat energy that you calculated in 2 above to determine the enthalpy change, ∆H, for
the reaction in terms of kJ/mol of phosphoric acid. This is your experimental value of ∆H.

4. Use a table of standard thermodynamic data to calculate the ∆H of neutralization for

phosphoric acid. Consider this the accepted value of ∆H. How does your experimental value
for ∆H compare to the accepted value?

5. Calculate the percent discrepancy between the calculated (accepted) value of the ∆H of
neutralization of H3PO4 and your experimental value.

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Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Data and Results 6
Data Analysis (Questions) 12 (1 + 3 + 3 + 3 + 2)
Conclusion 1
References 1__
Total = 25 marks

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 Vapor Pressure and
Heat of Vaporization

Experiment 14: Vernier # 34

When a liquid is placed in a container, and the container is sealed tightly, a portion of the liquid
will evaporate. The newly formed gas molecules exert pressure in the container, while some of
the gas condenses back into the liquid state. If the temperature inside the container is held
constant, then at some point equilibrium will be reached. At equilibrium, the rate of condensation
is equal to the rate of evaporation. The pressure at equilibrium is called vapor pressure, and will
remain constant as long as the temperature in the container does not change.
In mathematical terms, the relationship between the vapor pressure of a liquid and temperature is
described in the Clausius-Clayperon equation,
H vap 1
ln P C
R T
where ln P is the natural logarithm of the vapor pressure, ΔHvap is the heat of vaporization, R is
the universal gas constant (8.31 J/mol•K), T is the absolute, or Kelvin, temperature, and C is a
constant not related to heat capacity. Thus, the Clausius-Clayperon equation not only describes
how vapor pressure is affected by temperature, but it relates these factors to the heat of
vaporization of a liquid. ΔHvap is the amount of energy required to cause the evaporation of one
mole of liquid at constant pressure.
In this experiment, you will introduce a specific volume of a volatile liquid into a closed vessel,
and measure the pressure in the vessel at several different temperatures. By analyzing your
measurements, you will be able to calculate the ΔHvap of the liquid.

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OBJECTIVES
In this experiment, you will
Measure the pressure inside a sealed vessel containing a volatile liquid over a range of
temperatures.
Determine the relationship between pressure and temperature of the volatile liquid.
Calculate the heat of vaporization of the liquid.

Figure 1

MATERIALS
Vernier computer interface 20 mL syringe
computer two 125 mL Erlenmeyer flasks
Vernier Gas Pressure Sensor ethanol, CH3CH2OH
Temperature Probe 400 mL beaker
rubber stopper assembly 1 liter beaker
plastic tubing with two connectors hot plate

PROCEDURE
1. Obtain and wear goggles. CAUTION: The alcohol used in this experiment is flammable and
poisonous. Avoid inhaling the vapors. Avoid contact with your skin or clothing. Be sure that
there are no open flames in the room during the experiment. Notify your teacher immediately
if an accident occurs.

2. Use a hot plate to heat ~200 mL of water in a 400 mL beaker.

3. Prepare a room temperature water bath in a 1 liter beaker. The bath should be deep enough to
completely cover the gas level in the 125 mL Erlenmeyer flask.

4. Connect a Gas Pressure Sensor to Channel 1 of the Vernier computer interface. Connect a
Temperature Probe to Channel 2 of the interface. Connect the interface to the computer with
the proper cable.

5. Start the Logger Pro program on your computer. Open the file “34 Vapor” from the
Advanced Chemistry with Vernier folder.

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71
 6. Use the clear tubing to connect the white rubber stopper to the Gas Pressure Sensor. (About
one-half turn of the fittings will secure the tubing tightly.) Twist the white stopper snugly
into the neck of the Erlenmeyer flask to avoid losing any of the gas that will be produced as
the liquid evaporates (see Figure 1). Important: Open the valve on the white stopper.

7. Your first measurement will be of the pressure of the air in the flask and the room
temperature. Place the Temperature Probe near the flask. When the pressure and temperature
readings stabilize, record these values in the first column (Initial) of your data table.

8. Condition the Erlenmeyer flask and the sensors to the water bath.
a. Place the Temperature Probe in the room temperature water bath.
b. Place the Erlenmeyer flask in the water bath. Hold the flask down into the water bath to
the bottom of the white stopper.
c. After 30 seconds, close the valve on the white stopper.
9. Obtain a small amount of ethanol. Draw 3 mL of ethanol into the 20 mL syringe that is part
of the Gas Pressure Sensor accessories. Thread the syringe onto the valve on the white
stopper (see Figure 1).

10. Add ethanol to the flask.

a. Open the valve below the syringe containing the 3 mL of ethanol.
b. Push down on the plunger of the syringe to inject the ethanol.
c. Quickly pull the plunger back to the 3-mL mark. Close the valve below the syringe.
d. Carefully remove the syringe from the stopper so that the stopper is not moved.
11. Gently rotate the flask in the water bath for a few seconds, using a motion similar to slowly
stirring a cup of coffee or tea, to accelerate the evaporation of the ethanol.

12. Monitor and collect temperature and pressure data.

a. Click to begin data collection.
b. Hold the flask steady once again.
c. Monitor the pressure and temperature readings.
d. When the readings stabilize, click .
13. Add a small amount of hot water, from the beaker on the hot plate, to warm the water bath by
3-5°C. Use a spoon or a dipper to transfer the hot water. Stir the water bath slowly with the
Temperature Probe. Monitor the pressure and temperature readings. When the readings
stabilize, click .

14. Repeat Step 13 until you have completed five total trials. Add enough hot water for each trial
so that the temperature of the water bath increases by 3-5°C, but do not warm the water bath
beyond 40°C because the pressure increase may pop the stopper out of the flask. If you must
remove some of the water in the bath, do it carefully so as not to disturb the flask.

15. After you have recorded the fifth set of readings, open the valve to release the pressure in the
flask. Remove the flask from the water bath and take the stopper off the flask. Dispose of the
ethanol as directed.

16. Click to end the data collection. Record the pressure readings, as Ptotal, and the
temperature readings in your data table.
Advanced Chemistry with Vernier
72
17. Do not exit the Logger Pro program until you have completed 1-4 of the Data Analysis
section.

DATA TABLE
Initial Trial 1 Trial 2 Trial 3 Trial 4 Trial 5
Ptotal (kPa)

Pair (kPa)

Pvap (kPa)

Temperature
(°C)

DATA ANALYSIS
1. The Pair for Trials 2-5 must be calculated because the temperatures were increased. As you
warmed the flask, the air in the flask exerted pressure that you must calculate. Use the gas
law relationship shown below to complete the calculations. Remember that all gas law
calculations require Kelvin temperature. Use the Pair from Trial 1 as P1 and the Kelvin
temperature of Trial 1 as T1.
P1 P2
T1 T2

2. Calculate and record the Pvap for each trial by subtracting Pair from Ptotal.

3. Prepare and print a graph of Pvap (Y-axis) vs. Celsius temperature (X-axis).
a. Disconnect your Gas Pressure Sensor and Temperature Probe from the interface.
b. Choose New from the File menu. An empty graph and table will be created in Logger Pro.
c. Double-click on the x-axis heading in the table, enter a name and unit, then enter the five
values for temperature (°C) from your data table above.
d. Double-click on the y-axis heading in the table, enter a name and unit, then enter the five
values for vapor pressure from your data table above.
e. Does the plot follow the expected trend of the effect of temperature on vapor pressure?
Explain.

4. In order to determine the heat of vaporization, ΔHvap, you will first need to plot the natural
log of Pvap vs. the reciprocal of absolute temperature.
a. Choose New Calculated Column from the Data menu.
b. Create a column ln vapor pressure.
c. Create a second column, reciprocal of absolute temperature, 1/(Temperature (°C) + 273).
d. On the displayed graph, click on the respective axes, and then select ln vapor pressure to
plot on the y-axis, and reciprocal of absolute temperature to plot on the x-axis. Autoscale
the graph, if necessary.
e. Calculate the linear regression (best-fit line) equation for this graph. Calculate ΔHvap from
the slope of the linear regression.
f. Prepare and print a second graph.

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5. The accepted value of the ΔHvap of ethanol is 42.32 kJ/mol. Compare your
experimentally determined value of ΔHvap with the accepted value.

Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Data and Results 4
Data Analysis and Calculations 10 (graphs 2 + 2; calc. 3 + 3)
Exercise 4 (2 + 2)
Conclusion 1
References 1__
Total = 25 marks

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 Electrochemistry: Voltaic Cells

Experiment 15: Vernier # 20

In electrochemistry, a voltaic cell is a specially prepared system in which an oxidation-reduction

reaction occurs spontaneously. This spontaneous reaction produces an easily measured electrical
potential. Voltaic cells have a variety of uses.

In this experiment, you will prepare a variety of semi-microscale voltaic cells in a 24-well test
plate. A voltaic cell is constructed by using two metal electrodes and solutions of their respective
salts (the electrolyte component of the cell) with known molar concentrations. In Parts I and II of
this experiment, you will use a Voltage Probe to measure the potential of a voltaic cell with
copper and lead electrodes. You will then test two voltaic cells that have unknown metal
electrodes and, through careful measurements of the cell potentials, identify the unknown metals.
In Part III of the experiment, you will measure the potential of a special type of voltaic cell
called a concentration cell. In the first concentration cell, you will observe how a voltaic cell can
maintain a spontaneous redox reaction with identical copper metal electrodes, but different
electrolyte concentrations. You will then measure the potential of a second concentration cell and
use the Nernst equation to calculate the solubility product constant, Ksp, for lead iodide, PbI2.

Figure 1

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OBJECTIVES
In this experiment, you will
Prepare a Cu-Pb voltaic cell and measure its potential.
Test two voltaic cells that use unknown metal electrodes and identify the metals.
Prepare a copper concentration cell and measure its potential.
Prepare a lead concentration cell and measure its potential.
Use the Nernst equation to calculate the Ksp of PbI2.

MATERIALS
Vernier computer interface 0.10 M copper (II) nitrate, Cu(NO3)2, solution
computer 0.10 M lead (II) nitrate, Pb(NO3)2, solution
Voltage Probe 1.0 M copper (II) sulfate, CuSO4, solution
three 10 mL graduated cylinders 0.050 M potassium iodide, KI, solution
24-well test plate 1 M potassium nitrate, KNO3, solution
string 0.10 M X nitrate solution
Cu and Pb electrodes 0.10 M Y nitrate solution
two unknown electrodes, labeled X and Y steel wool
150 mL beaker plastic Beral pipets

PRE-LAB EXERCISE
Use the table of standard reduction potentials in your text, or another approved reference, to
complete the following table. An example is provided.
° °
Electrodes Half-reactions E E cell
2+ –
Zn Zn(s) → Zn + 2e +0.76 V
2+ – +1.10 V
Cu Cu + 2e → Cu(s) +0.34 V
Cu
Pb

Pb
Ag

Pb
Mg

Pb
Zn

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76
 PROCEDURE
o
Part I Determine the E for a Cu-Pb Voltaic Cell
1. Obtain and wear goggles.

2. Use a 24-well test plate as your voltaic cell. Use Beral pipets to transfer small amounts of
0.10 M Cu(NO3)2 and 0.10 M Pb(NO3)2 solution to two neighboring wells in the test plate.
CAUTION: Handle these solutions with care. If a spill occurs, ask your instructor how to
clean up safely.

3. Obtain one Cu and one Pb metal strip to act as electrodes. Polish each strip with steel wool.
Place the Cu strip in the well of Cu(NO3)2 solution and place the Pb strip in the well of
Pb(NO)3 solution. These are the half cells of your Cu-Pb voltaic cell.

4. Make a salt bridge by soaking a short length of string in a beaker than contains a small
amount of 1 M KNO3 solution. Connect the Cu and Pb half cells with the string.

5. Connect a Voltage Probe to Channel 1 of the Vernier computer interface. Connect the
interface to the computer with the proper cable.

6. Start the Logger Pro program on your computer. Open the file “20 Electrochemistry” from
the Advanced Chemistry with Vernier folder.

7. Measure the potential of the Cu-Pb voltaic cell. Complete the steps quickly to get the best
data.
a. Click to start data collection.
b. Connect the leads from the Voltage Probe to the Cu and Pb electrodes to get a positive
potential reading. Click immediately after making the connection with the
Voltage Probe.
c. Remove both electrodes from the solutions. Clean and polish each electrode.
d. Put the Cu and Pb electrodes back in place to set up the voltaic cell. Connect the Voltage
Probe to the electrodes, as before. Click immediately after making the connection
with the Voltage Probe.
e. Remove the electrodes. Clean and polish each electrode again.
f. Set up the voltaic cell a third, and final, time. Click immediately after making the
connection with the Voltage Probe. Click to end the data collection.
g. Click the Statistics button, . Record the mean in your data table as the average
potential. Close the statistics box on the graph screen by clicking the X in the corner of the
box.
o
Part II Determine the E for Two Voltaic Cells Using Pb and Unknown Metals
8. Obtain a small amount of the unknown electrolyte solution labeled “0.10 M X” and the
corresponding metal strip, X.

9. Use a Beral pipet to transfer a small amount of 0.10 M X solution to a well adjacent to the
0.10 M Pb(NO3)2 solution in the test plate.

10. Make a new salt bridge by soaking a short length of string in the beaker of 1 M KNO3
solution. Connect the X and Pb half cells with the string.

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11. Measure the potential of the X-Pb voltaic cell. Complete this step quickly.
a. Click to start data collection.
b. Connect the leads from the Voltage Probe to the X and Pb electrodes to get a positive
potential reading. Click immediately after making the connection with the
Voltage Probe.
c. Remove both electrodes from the solutions. Clean and polish each electrode.
d. Set up the voltaic cell again. Connect the Voltage Probe as before. Click
immediately after making the connection with the Voltage Probe.
e. Remove the electrodes. Clean and polish each electrode again.
f. Test the voltaic cell a third time. Click immediately after making the connection
with the Voltage Probe.
g. Click to end data collection.
h. Click the Statistics button, . Record the mean in your data table as the average potential
and then close the statistics box on the graph screen by clicking the X in the corner of the
box.
12. Repeat Steps 8-11 using the unknown and its corresponding electrolyte solution labeled “Y”.

Part III Prepare and Test Two Concentration Cells

13. Set up and test a copper concentration cell.
a. Prepare 20 mL of 0.050 M CuSO4 solution by mixing 1 mL of 1.0 M CuSO4 solution
with 19 mL of distilled water.
b. Set up a concentration cell in two wells of the 24-well test plate by adding 5 mL of
0.050 M CuSO4 solution to one well and 5 mL of 1.0 M CuSO4 solution to a neighboring
well. Use Cu metal electrodes in each well. Use a KNO3-soaked string as the salt bridge,
as in Parts I and II.
c. Click to start data collection.
d. Test and record the potential of the concentration cell in the same manner that you tested
the voltaic cells in Parts I and II.
14. Set up a concentration cell to determine the solubility product constant, Ksp, of PbI2.
a. Prepare 10 mL of 0.050 M Pb(NO3)2 solution by mixing 5 mL of 0.10 M Pb(NO3)2
solution with 5 mL of distilled water.
b. Mix 9 mL of 0.050 M KI solution with 3 mL of 0.050 M Pb(NO3)2 solution in a small
beaker. In this reaction, most of the Pb2+ and I– will form the precipitate PbI2, but a small
amount of the ions will remain dissolved.
c. Set up the half cells in neighboring wells of the 24-well test plate. Place 5 mL of 0.050 M
Pb(NO3)2 solution in one half cell, and 5 mL of the PbI2 mixture, from the small beaker,
into an adjacent half cell. Use Pb electrodes in each half cell. Use a KNO3-soaked string
as the salt bridge.
d. Test and record the potential of the cell in the same manner that you tested the voltaic
cells and the copper concentration cell.
15. Discard the electrodes and the electrolyte solutions as directed. Rinse and clean the 24-well
plate. CAUTION: Handle these solutions with care. If a spill occurs, ask your instructor
how to clean up safely.

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DATA TABLE

Results of Parts I and II Cu/Pb X/Pb Y/Pb

Average cell potential (V)

Results of Part III Cu concentration Pb/PbI2

Average cell potential (V)

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DATA ANALYSIS
1. (Part I) Compare the average cell potential, for your Cu/Pb cell, with the E°cell that you
calculated in the pre-lab exercise. Explain why your cell potential is different from the text
value.

2. (Part II) The unknown metals X and Y were either magnesium, silver, or zinc. Use the text
value for the reduction potential of Pb and the measured cell potentials for the unknowns to
identify X and Y.

3. (Part III) Use the Nernst equation to calculate the theoretical value of E of the copper-
concentration cell and compare this value with the cell potential that you measured.

4. (Part III) Use the Nernst equation and the information that you collected about the Pb/PbI2
cell to complete the following calculations.
a. Use the cell potential for the Pb-PbI2 cell and the known [Pb2+] to calculate the [Pb2+] in
equilibrium with PbI2.
b. Use the original diluted [Pb2+] and [I-] to calculate the [I-] in solution.
c. Use your data to calculate the Ksp of PbI2
d. The accepted value of the Ksp of PbI2 is 9.8 × 10–9. How does your experimental Ksp of
PbI2 compare with the accepted value?
Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Prelab Exercise 2
Data + Results 4
Calculations (Questions) 12 (6 + 3 + 3)
Conclusion 1
References 1_______
Total = 25 marks

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 Electroplating

Experiment 16: Vernier # 21

In this experiment, you will conduct, observe, and measure the process of electroplating. This
process is used to deposit a layer of metal, such as chromium, copper, or gold, onto another
metal. As a commercial process, electroplated coatings are used to improve appearance, resist
corrosion, or improve hardness of metallic surfaces. This experiment describes one method of
producing a copper coating on a brass key or other suitable metallic object.

You will prepare an electrochemical cell by using a copper strip as the cathode (positive
terminal) and a brass key as the anode (negative terminal). The electrodes are immersed in a
solution containing acidified copper (II) sulfate. As you apply a potential to the electrodes, you
will be effectively transferring Cu atoms from the anode to the surface of the brass key.

In this experiment, you will use one application of Faraday’s law, stated in equation form below.
I t ( MM )
Mass deposited at an electrode
96,500 n
I is the current in amperes; t is the time that the current is applied, in seconds; MM is the molar
mass of the element that is deposited; n is the number of moles of electrons/mol; and 96,500 is ₣,
the Faraday constant.

Figure 1

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OBJECTIVES
In this experiment, you will
Prepare and operate an electrochemical cell to plate copper onto a brass surface.
Measure the amount of copper that was deposited in the electroplating process.
Calculate the amount of energy used to complete the electroplating process.

MATERIALS
Vernier computer interface electrolyte solution (CuSO4 in H2SO4)
computer vinegar
Vernier Current Probe 1 cm × 10 cm copper strip
1.5 volt DC power supply brass key
four connecting wires with alligator clips solid sodium chloride, NaCl
steel wool balance, 0.001 g precision
two 250 mL beakers bare copper wire, 20-22 gauge
distilled water

PROCEDURE
1. Obtain and wear goggles.

2. Use steel wool to clean a brass key and a strip of copper, which will be the electrodes of the
electrochemical cell.

3. Mix 3 g of NaCl with 15 mL of vinegar in a 250 mL beaker. Wash the key and the copper
strip in this salt-vinegar solution. Rinse the key and copper strip with distilled water and dry
each metal piece.

4. Use an analytical balance to determine the mass of the key and the mass of the copper strip.
Record these two masses in your data table.

5. Fill a 250 mL beaker about ¾ full with the electrolyte solution. CAUTION: The electrolyte
solution in this experiment is prepared in H2SO4 and should be handled with care.

6. Attach a 7 cm length of bare copper wire to the brass key to act as a handle. Connect the wire
to the alligator clip for the anode, so that the key will be completely immersed in the
electrolyte solution but the alligator clip will not be immersed. Connect the copper strip to
the positive lead on the cell. Important: You will not place the electrodes in the cell until
Step 10.

7. Obtain a DC power supply and a Vernier Current Probe. Use connecting wires, with alligator
clips, to connect the DC power supply, Current Probe, and the electrodes. See Figure 1 for
the proper setup of the wiring. Important: You will not place the electrodes in the cell until
Step 10.

8. Connect the Current Probe to Channel 1 of the Vernier computer interface. Connect the
interface to your computer with the proper cable.

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 9. Start the Logger Pro program on your computer. Open the file “21 Electroplating” from the
Advanced Chemistry with Vernier folder.

10. Place the key and the copper strip into the electrolyte solution in the cell. Make sure that the
key is completely immersed in the solution, and keep the two electrodes as far apart as
possible.

11. Turn on the DC power source and check the sensor readings. The initial current should be in
the 0.2-0.6 A range. If the current is not in this range, check with your instructor before
proceeding.

12. Click to begin the data collection. Observe the electrolysis. Note the slow deposition
of copper on the surface of the key. The data collection will run for 30 minutes.

13. When the data collection is complete, turn off the DC power source and carefully remove the
copper strip and key from the electrolyte solution. Rinse the two metals with distilled water.
Dry the copper strip and key so as not to remove copper.
14. Analyze the graph of your data to determine the average current that was applied during the
electrolysis. Click the Statistics button, . Record the mean in your data table as the average
current.

15. Measure and record the mass of the dry copper strip and key.

16. Discard the electrolyte solution and take care of the electrochemical cell as directed by your
instructor.

DATA TABLE

Initial mass of copper electrode (g)

Final mass of copper electrode (g)

Initial mass of key (g)

Final mass of key (g)

Average current (A)

Time of current application (s)

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DATA ANALYSIS
1. Calculate the number of coulombs of charge passed through the electrolytic cell.

2. Calculate the theoretical number of moles of copper that should have plated out onto the
brass key.

3. Calculate the actual number of moles of copper that plated out.

4. Calculate the percent yield of copper.

5. Suggest the sources of error in your experiment.

6. Write the oxidation and reduction half-reactions for this process.

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Markscheme
Aim 1
Abstract 2
Procedure (Summary) 2
Data Table 3
Data Analysis (Questions) 12 (1 + 2 + 3 + 2 + 2 + 2)
Discussion 3
Conclusion 1
References 1
Total = 25 marks

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