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CHM104

Chemistry 1A
FACULTY OF SCIENCE

Laboratory Manual
201030

*CHM104*
Chemistry 1A

CHM104 Laboratory Manual

Faculty of Science

Written and compiled by


Dr Ian Barnard

Revised by
Dr Michael Antolovich
Dr John H. Beard
Dr Andrea Bishop
Educational designer
Jen Thompson

Produced by the Division of Learning and Teaching Services, Charles Sturt University, Albury -
Bathurst - Wagga-Wagga, New South Wales, Australia.

Revised 1986
Reprinted 1990, 1991, 1993
Revised 1994, 1995, December 1997, December 1998, December 1999,
December 2000, December 2001, November 2002, November 2003,
November 2004, November 2005
Reprinted November 2006
Revised November 2007
Reprinted November 2008
Revised January 2010

Printed at Charles Sturt University

© Charles Sturt University

Previously published material in this book is copied on behalf of Charles Sturt University pursuant to
Part VB of the Commonwealth Copyright Act 1968.

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Contents

Page

General notes 1 
The aims of the practical program 1 
Learning outcomes 1 
How to use the manual 1 
Assessment of laboratory work 2 
How to use the laboratory 3 
Laboratory safety 3 
Safety rules 5 

Experiment 1:  Colorimetric determination of copper 7 

Experiment 2:  Volumetric analysis 13 

Experiment 3:  A series of chemical changes 19 

Experiment 4:  Classification of matter 25 

Experiment 5:  Chemical equilibria 33 

Experiment 6:  Acid-base equilibria in aqueous solutions 37 

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General notes

The aims of the practical program


Chemistry is an experimental science. The current theories on the nature of
atoms, molecules and bonding that are used to explain the behaviour of bulk
matter, are based on experimental data. The methods and processes required to
generate, collect and record such data are the valuable, transferable skills that we
aim to develop during these laboratory sessions.

Learning outcomes

When you have successfully completed this subject you should be able to:

• understand the language of chemistry;


• calculate chemical amounts of matter;
• apply known physical laws to appropriate situations and perform the related
calculations correctly;
• understand the molecular behaviour of matter and how this relates to the
observed macroscopic (bulk) properties;
• understand the forms matter assumes, in terms of the bonding in its
molecules;
• perform calculations involving quantities of matter in solution;
• understand the properties of acids, bases, and solutions;
• appreciate the nature of chemical equilibria and be able to calculate
chemical quantities in reactions that have reached equilibrium;
• apply basic practical skills.

How to use the manual

Each experiment is set out under a number of headings:

Outline

This is a brief statement of the overall point of the exercise.

Objectives

These list many of the concepts and skills which you should have mastered on
completing the exercise. If you have any difficulty with any of these objectives
you should discuss them with your demonstrator.

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Discussion

This section includes theory relevant to the practical exercise. It must be worked
through before attempting the practical work.

Procedure

The actual practical work to be undertaken is set out in stepwise fashion in this
section. It is essential that this be read and complete the preliminary
questions BEFORE attending the practical session. You should relate the
procedural steps to the discussion section and the objectives. You should then be
able to perceive the point of the exercise. The value in doing this is that your time
in the laboratory will be spent most efficiently and you will enjoy a sense of
purpose in your practical endeavours. Practical work should never reduce to
‘recipe-following’.

Result sheet

It is essential that you record your results in ink on the result sheet at the time
of the experiment. Marks will be deducted for use of pencil and liquid paper.
At any later stage you must be confident that the results recorded were honest,
not a later inclusion of what you thought may possibly have happened. The
result sheet must be signed and dated by your demonstrator at the conclusion of
the practical work.

Post work

In most cases this section of the exercise should be completed during the practical
session. In some cases, the calculations involved in an experiment take some time
which is best found outside the time allocated for practical work. In others, some
questions are set to test your understanding of the concepts involved in the
particular practical exercises.

Assessment of laboratory work

Practical work is allocated 20% of the total assessment for Chemistry 1A. Details
are provided in the Subject Outline.

Attendance at practical sessions is compulsory. Any student who attends less than
80% of the time allocated to practical work without adequate explanation (e.g.
medical certificate for illness) will be automatically awarded an FL grade for
Chemistry 1A.

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How to use the laboratory

The following points are listed to help you to work efficiently in the laboratory.

• Communal general purpose apparatus is kept in the cupboards under the


bench spaces.
• Common laboratory reagents (chemicals) are placed on the shelves above
the benches and on the side walls of the laboratory. If a reagent bottle is
empty take it to the service hatch for refilling by the laboratory staff.
• All other apparatus and reagents are available at the service hatch.
• You are responsible for the cleanliness of your workspace and the apparatus
you use.
• Balances and any other equipment you use must be treated with care and not
contaminated by any chemicals. Wipe up any accidental spillage
immediately.
• It is essential to recap each reagent bottle with its correct cap after each use.
• Solid wastes must be placed in the bins provided.
• Organic liquids must be disposed of in the organic residues bottles placed in
the fume cupboards.
• Broken glass should be placed in the bins labelled for that purpose.

If you are at all unsure about any procedure, ask your demonstrator.

Laboratory safety

A chemical laboratory should be a safe place in which to work. Most accidents


arise from carelessness or ignorance of appropriate precautions to be taken when
carrying out particular laboratory operations. It is wise, in the absence of specific
knowledge, to assume all chemicals to be potentially harmful and to have a
demonstrator check the assembly of any apparatus with which you are unfamiliar
before you use it.

To help you become a safe laboratory worker, some hazards commonly found in
chemistry laboratories are mentioned below. These are followed by a set of rules
which must be obeyed at all times by students working in the chemistry laboratories.

Hazards

a. Laboratory equipment
• All unfamiliar equipment, e.g., distillation apparatus, gas cylinders,
should be regarded as hazardous. Check with a demonstrator
before use.
• Never use cracked or badly worn glassware. Obtain a replacement
from the service counter.

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b. Dangerous chemicals
Gases and vapours
• Entry routes for gases and vapours are through the lungs, eyes, skin
and mouth.
• Some which attack eyes and lungs are Cl2, Br2, NH3, NO2, SO2.
• Those which are toxic when inhaled include H2S, HCN, CO, Hg.
• Vapours of any flammable liquid and H2 and CO can form explosive
mixtures with air.
• Any reaction from which a gas issues should be performed under a
fume hood, as should any reaction known to involve even minute
amounts of the gases listed above.

Liquids
• Entry routes for liquids are through the skin, eyes and mouth.
• Liquids or solutions which are strongly acidic, strongly basic or
strongly oxidizing can cause external damage particularly to eyes.
Liquids containing a halogen often behave similarly.
• Affected areas of the body should be washed with copious quantities
of water.
• Some liquids decompose explosively when heated. A common
example is hydrogen peroxide H2O2.
• Liquids boiling in open containers can superheat and vaporise
explosively. A boiling chip (porous pot), placed in the liquid before
heating is commenced, reduces this hazard.

Solids
• Most solid chemicals are toxic to some extent.

• Entry routes for solids are through the lungs, eyes, skin and mouth.

c. Materials Safety Data Sheets (MSDS)

MSDSs are available in the laboratory, at the safety station. It should be


considered a regular part of your pre-lab preparation to read the MSDSs
relevant to the experiment that you will be undertaking.

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Safety rules

The following are forbidden in the laboratory:

1. Working without supervision by a member of the teaching staff.

2. Conducting unauthorised experiments.

3. Skylarking or behaving mischievously.

4. Smoking, drinking or eating.

5. Attempting any electrical repairs however simple.

6. Pipetting by mouth. (Use a pipette filler to apply suction to a pipette.)

You are obliged to:

1. Wear appropriate clothing, including fully enclosed footwear. Footwear


must cover the toes, heel and upper and lower foot. It is compulsory to
wear a protective white coat or equivalent protective clothing.

2. Wear safety glasses approved to Australian Standard AS/NZ 1337 at all


time in the laboratory. These will not be supplied - you are expected to
provide your own. Note: Sunglasses and prescription glasses are not
acceptable. If prescription glasses required Australian Standard approved
over-glasses must be worn.

3. Report all accidents, however slight, to the supervisor or first aid officer .

4. Familiarise yourself with the location and operation of safety equipment in


the laboratory.

5. Dispose of all waste appropriately.

To be handed in to supervisor:

 ---------------------------------------------------------------------------------
I have read and agree to abide by the rules set out above.
Signed: __________________________________

Print name: _____________________________

Date: ___________

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Experiment 1: Colorimetric determination of copper

Outline

A set of standard concentrations of copper (II) sulfate are converted to the


intensely coloured copper (II) tetraamine complex, [Cu(NH3)4]2+. These are used
to establish a calibration plot of absorbance versus copper concentration. A
sample of runoff water from a fertilised field is treated similarly to the standards
and its copper content is obtained colorimetrically using the calibration plot. The
copper content of the sample is then compared to the Environmental Protection
Authority’s prescribed ‘safe’ levels.

Objectives

On successfully completing this experiment you should be able to:


• outline how a colorimeter works;
• define the terms: transmittance, percent transmittance and absorbance;
• apply the Beer-Lambert Law, A = εbc;
• perform a colorimetric analysis;
• carry out solution stoichiometry with improved skills;
• be able to construct and use a calibration plot.

Discussion

Colorimetric analysis is a sensitive method for the determination of the amount of


coloured species in solution.

It is a common observation that the intensity of colour in a solution increases as


we increase the concentration of coloured species. Our eyes alone are relatively
crude measuring instruments. A colorimeter, as its name implies, is an instrument
that measures colour intensity with good sensitivity and precision.

A block diagram of a colorimeter is given below.

Source Wavelength selector Sample Detector Display

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The source emits all the colours of white light. The wavelength selector (a
monochromator or filter) selects a particular wavelength (really a very narrow band
of wavelengths) which it is known is absorbed by the sample (analyte). Some
fraction of that wavelength of light passing through the sample will be absorbed by
the sample. For a fixed source intensity, P0, the intensity of the light emerging from
the sample, P, is determined by the concentration of analyte. The higher the
concentration, the more light is absorbed by the sample and hence the lower is P.
The detector, a photomultiplier tube (PMT), converts the incoming light signal, P,
into an outgoing electrical signal which can be very precisely measured.

The display gives a reading of transmittance (T), percent transmittance (%T) or


absorbance (A) which are defined as
P
T = ,
P0
%T = 100T
A = – log T

If the sample absorbs none of the selected wavelength, then P = Po


∴ T = 1, %T = 100 and A = 0

If the sample absorbs all of the selected wavelength, then P = 0


∴ T = 0, %T = 0 and A = ∞.

Colorimetry can be used as a quantitative analysis technique because of the


relationship between A and the concentration of analyte, c. This relationship, which
holds for monochromatic (single wavelength) light is the Beer-Lambert Law:
A = εbc
where A = absorbance (no units).
ε = molar absorptivity (L cm–1mol–1)
b = cell path length (cm)
c = analyte concentration (mol L–1)

The molar extinction coefficient of an analyte is a constant for a particular


wavelength and is a measure of the strength of absorbance of the analyte at that
wavelength. The call path length is the distance that the source light must travel
to pass though the sample. In any particular analysis, the wavelength is fixed i.e.
ε is constant. A fixed cell path length (usually 1 cm) is used i.e. b constant.
Therefore A ∝ c, so a plot of A versus c for different concentrations gives a
straight line through the origin.

Hence, a standard curve can be constructed that relates A to the concentration of


analyte present in a solution. Experimentally, we use a set of known standard
solutions of analyte to construct such a calibration plot. Standard solutions can be
prepared by volumetric dilutions of a stock solution of accurately known
concentration (see Using a volumetric flask, below). The absorbance of the
unknown solution is then measured and the plot used to determine the unknown
concentration in a sample solution.

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X
X
X
A X

c
A calibration plot determined at a fixed analysis wavelength.

Clearly, colorimetry relies on the analyte being coloured. Many substances are
naturally coloured and so can be directly analysed by colorimetry. However, even
those that are not coloured (or are so feebly coloured that analysis is very
difficult) can often be made intensely coloured by reaction with another species.
This is the case in this experiment.

Aqueous CuSO4 solutions have a very pale colour at low concentrations and so
cannot be directly analysed spectrophotometrically. However, the complex ion
[Cu(NH3)4]2+ produces intensely coloured solutions in water that absorb light in
the visible region. The copper (II) ions in a copper sulfate solution can be
converted to the intensely coloured tetraamine complex by the addition of
concentrated aqueous ammonia.

Cu2+(aq) + 4NH3(aq) → [Cu(NH3)4]2+(aq)


pale blue intense blue
A series of copper sulfate standard solutions may be prepared and then converted
to the copper tetraamine complex. The intense blue complex ion absorbs strongly
at 600 nm and can therefore be analysed by colorimetry at that wavelength.

Using a volumetric flask

A volumetric flask is accurately calibrated to a fixed


volume (e.g. 10 mL, 25 mL etc.). These are quite different
to conical flasks which sometimes have painted calibration
marks that are usually grossly incorrect. The material and
solvent are normally added to the flask and mixed. When
all the material has dissolved, the solution is ‘made up to
the mark’. There is a single etched line on the neck of the
flask. The solvent is very carefully added until the bottom
of the meniscus lines up with this mark; use a pasture
pipette rather than a wash bottle. If too much solvent is
added, the flask will have to be thoroughly rinsed with
solvent and the process started again. It is also important to mix the solution by
inverting the flask a number of times. Note that the lid must be the right size to
prevent spillage. Do NOT use your thumb or finger!!

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Procedure

Preparation of standard and sample solutions

After you have been shown how to use an analytical balance use it to weigh
approximately 1.2 g of solid CuSO4·5H20 into a beaker. Record the actual mass
to 0.0001 g.

Dissolve in a little water and transfer quantitatively to a 100 mL volumetric


flask, labelled ‘Cu stock’ solution. Make up to volume with deionised water and
ensure thorough mixing.

Label five 50 mL volumetric flasks 1, 2, 3, 4 and 5. Transfer appropriate volumes


of the stock solution to each of these flasks by pipette. Refer to Table 1.1 for the
volumes of stock solution to be added.

Make up to the mark with deionised water, making sure the solutions are well mixed.

Label six 15 cm test tubes S0, S1, S2, S3, S4, S5 and pipette 5.00 mL of the
respective solutions from the volumetric flasks into them. S0 should contain
deionized water only.

Obtain a sample of the run-off water for analysis.

Label three test tubes X1, X2 and X3. Pipette 5.00 mL of the same test water
sample into each of these test tubes.

Add 0.4 mL of concentrated ammonia solution, NH3(aq) †, to each test tube from
the dispenser. Caution: Avoid inhaling ammonia. Mix thoroughly by gently
agitating the test tubes (consult a demonstrator if you are unsure how to proceed).

Colorimetric analysis

Set the spectrophotometer wavelength to 600 nm (consult a demonstrator, if you


need help).

Zero the instrument using your blank solution.

Measure each of the standard solutions in turn, and record the absorbance values
directly in Table 1.1.

Measure each of the test solutions in turn, and record the absorbance values
directly in Table 1.2.

Confirm that the absorbance reading obtained for the samples fall within the range
of absorbance values recorded for your standard solutions. (If not, consult a
demonstrator).

Discard solutions in the marked container.


__________________________
† See MSDS

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Data analysis

Calculate the molar (moles per litre) concentration of the stock standard solution
prepared. Record your working and answer on the result sheet.

The stock standard solution was diluted volumetrically to prepare the standards.
Use the concentration of the stock standard solution to calculate the concentration
of copper (II) in each of the 50 mL standard solutions, S0 to S5. Record your
answers in Table 1.1 of the result sheet.

On graph paper (available from the service hatch) prepare a properly labelled
calibration plot of absorbance against copper concentration for S0 to S5.

Using the absorbance values recorded for the water sample solutions and the
calibration plot to determine the copper concentration for each of X1,X2 and X3.
Record in Table 1.2 of the result sheet.

Calculate a mean value for [Cu2+] in your unknown. As the error, quote the
greatest absolute deviation from the mean.

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Experiment 2: Volumetric analysis

Outline

A standardisation titration is performed to accurately determine the concentration


of a sodium hydroxide solution. The sodium hydroxide solution is then used in an
acid-base titration, performed to determine the concentration of acetic acid in
vinegar.

Objectives

On completing this experiment you should be able to:

• distinguish between qualitative and quantitative analysis;

• define the terms as used in volumetric analysis: primary standard, titration,


titrant, indicator, end point, equivalence point;

• list the criteria a substance should meet to serve as a primary standard;

• list the criteria to be met by a chemical reaction for it to suit volumetric


analysis.

• perform a titration employing correct technique and obtain reproducible


results;

• perform calculations based on solution stoichiometry.

Discussion

Before beginning this experiment you should read the section on solution
stoichiometry in Module 1.

There are two aspects to the analysis of a substance. Analysis of a substance to


determine its chemical nature (i.e. to identify it) is called qualitative analysis.
Analysis which seeks to determine how much of the substance is present in a
sample is called quantitative analysis. Volumetric analysis is a quantitative
analysis technique in which the amount of substance is determined from the
measurement of volumes. Volumetric analysis involves the technique called
titration. Titration is the addition from a burette of a solution of one reactant (this
reactant from the burette is sometimes called the titrant and the volume of titrant
delivered from the burette is called its titre) to a known mass or a measured
volume of a solution of another reactant until the stoichiometrically equivalent
number of moles of the reactants have been combined. This point (the point at
which just the correct amount of titrant has been added to completely react with

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the reactant in the flask) is called the equivalence point. To know when we have
reached the equivalence point we use a substance called an indicator which
undergoes a colour change in the region of the equivalence point. The point at
which the indicator changes colour is called the end point of the titration. It is
important that we choose an indicator so that the end point coincides with the
equivalence point of the titration.

There are certain criteria to be met by a reaction for it to be successfully used for a
titration:

• the reaction rate should be fast


• the reaction should go to completion
• the reaction should be free from side reactions
• a suitable indicator must be available to signal the equivalence point.

The discussion given below meets these criteria and introduces the remaining
aspects of volumetric analysis necessary for you to complete the experimental
work.

In this experiment, the exact concentration of a solution of acetic acid, known to


be about 0.1M is to be determined by titration with sodium hydroxide. To
perform a useful titration, we must know the concentration of sodium hydroxide
accurately and precisely. This is achieved by the procedure known as
standardization. Standardization uses a primary standard to determine the
precise concentration of another solution.

A primary standard is selected having the following properties:

• a solid of high purity


• stable e.g. not affected by moisture, CO2 etc. in the air
• has a relatively high molecular weight to minimise weighing errors
• meets the reaction criteria listed previously for titration.

For standardizing sodium hydroxide, a suitable primary standard is hydrochloric


acid. Recall that hydrochloric acid is a solution of H+ and Cl– ions and sodium
hydroxide solution contains Na+ and OH– ions. When the two solutions are
mixed, the following reaction occurs, which may be written in several ways:

HCl (aq) + NaOH (aq) → H2O (l) + NaCl (aq)

or, as the total ionic equation:

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) → H2O (l) + Na+(aq) + Cl-(aq)

or, as the net ionic equation:

H+(aq) + OH-(aq) → H2O (l)

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The reaction is essentially instantaneous and completely to the exclusion of any


other reaction.

If we accurately know the concentration of the hydrochloric acid, we can use the
HCl(aq) as a standard. For example, let us say that the concentration of
hydrochloric acid to be used in the experiment is 0.0894M HCl .
i.e. [HC1] = [H + ] = 0.0894 M
Note: Unless specified otherwise, square brackets around a substance means
concentration in moles per litre.

This will have been determined by the technical staff prior to the experiment,
using a primary standardization method.

Using a pipette, a precise volume of the standardized HCl, in this example 2.00
mL, is delivered into a conical flask and indicator added. Using a burette,
NaOH(aq) is run into the conical flask until the end point is reached. The volume
added from the burette in this example is 2.30 mL. Assuming that we chose an
indicator so that the end point coincided with the equivalence point, we can
calculate the concentration of the NaOH(aq) as follows:

2.00
Number of mole H+ added = L × 0.0894mol / L
1000

= 1.79 x 10-4 mol

Since the reaction is H + + OH − → H 2 O ,


we know that H+ combines with OH- on a 1:1 basis
∴ the moles of H+ added (1.79 x 10-4 mol) will react with the same number of
moles of OH- (1.79 x 10-4 mol)

This amount was contained in the titre delivered from the burette, i.e. 2.30 mL.
2.30
∴ Concentration of NaOH = 1.79 × 10 − 4 mol ÷ L
1000
= 0.0778 mol/L
or 0.0778 M

Similarly, the standardized sodium hydroxide solution may then be used to


determine the concentration of acetic acid in a sample.

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Acid-base titration
Procedure

i. Standardization of sodium hydroxide† solution

Check with your demonstrator on the correct use of burettes.

Prepare about 50 mL of approximately 0.1M NaOH† by 20-fold dilution of 2M


NaOH in a plastic specimen jar. A measuring cylinder will give sufficient
precision for the required volume measurements; make sure to mix the solution
well.

Note - You will need this solution for both parts i and ii of this experiment.

Use a small volume of this approx. 0.1M NaOH solution to rinse a burette. Fill
this burette to somewhere near the 0 mL mark and record the reading to the
nearest 0.01 mL.

Place approximately 1 mL of the approx. 0.1M NaOH solution in a small test tube
and add 2 drops of bromothymol blue† indicator. Record the colour of the
indicator in base.

Record the molarity of the standardized hydrochloric acid†. Using a volumetric


pipette transfer 3.00 mL of the standardized hydrochloric acid to a clean, not
necessarily dry, 20-30 mL conical flask. Add just sufficient bromothymol blue†
indicator for its colour to be evident. Record the colour of the indicator in acid.

Perform a rough titration as follows:


While swirling the conical flask, run the base in from the burette rapidly until a
colour change is observed. Record the colour of the indicator in the now basic
solution and the burette reading to the nearest 0.01 mL. Calculate the volume of
base added in this rough titration.

Repeat the titration precisely now, using a fresh 3.00 mL aliquot (sample) of the
acid but run the base in rapidly only until 0.5 mL less has been added than in the
rough titration. Continue adding the base dropwise until an indicator hue
intermediate between that found in acid and in base is obtained. Record the
burette reading. Calculate the volume of base used in this precise titration.

Perform a second precise titration and record your results. If the volumes of base
used in the two precise titrations are not concordant to within 0.02 mL, perform
further titrations until this repeatability is achieved. Calculate the molarity of the
sodium hydroxide†.

ii. Determination of the concentration of acetic acid† in vinegar

Using a volumetric pipette transfer 5.00 mL of vinegar to a 50.00 mL volumetric


flask and make up to the mark. Stopper the volumetric flask and mix well. Call
this the acetic acid solution.

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Pipette accurately 3.00 mL of the acetic acid solution into a clean conical flask
and 2 drops phenolphthalein† indicator. Record the indicator colour in acid.

Place approximately 1 mL of standardized NaOH† solution in a small test tube


and add 2 drops phenolphthalein† indicator. Record the indicator colour in base.

Perform a rough titration using standardized sodium hydroxide† as titrant. As in


part i, carry out at least two precise titrations until you obtain concordant results.
Record your results and calculate firstly the concentration of acetic acid in the
dilute solution, then the concentration of acetic acid† in vinegar.

__________________________
† See MSDS

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Experiment 3: A series of chemical changes

Outline

Copper metal is recovered, via a series of chemical changes, from a sample of


copper(II) chloride.

Objectives

On successfully completing this experiment you should be able to:


• differentiate between a physical and a chemical change;
• understand the need for care and use of proper technique to obtain sensible
results in laboratory operations;
• use a top loading balance;
• perform a separation by filtration;
• use the mole as the chemical unit of amount;
• perform simple calculations involving molarities;
• calculate percent yields for chemical reactions;
• appreciate that a knowledge of solubility rules can simplify the task of
planning the conversion of one compound to another.

Discussion
Before beginning this experiment you should read the topic on Stoichiometry.
Substances are characterised (identified) by their properties. The properties of
substances can be classified as physical properties or chemical properties.
Physical properties of a substance are those which do not involve changing the
substance into another. For instance, the temperature at which ice melts to form
liquid water is a physical property of water since the change is a physical change;
both ice and liquid water have the same chemical composition, H2O. Chemical
properties of a substance are those which involve a chemical change, i.e. the
conversion of the substance to another substance. For instance, the ease with
which a substance burns is a chemical property since, in burning, the substance
chemically combines with oxygen.
In this experiment the metal, copper, is obtained by a series of chemical changes
from copper(II) chloride†.
__________________________
† See MSDS

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Quantitative transfer

Complete transfer of material without loss. Solids are often weighed on a weigh
boat or watch glass and transferred into a beaker or flask. There is no point
carefully weighing something to 4 decimal places only to tap most of it into a
beaker and then throwing the rest away.

If transferring into a volumetric flask, rinse a glass funnel and place it in the flask.
The solid is carefully transferred to the funnel and then any remaining material is
washed from the weigh boat into the funnel (a wash bottle may be used). Also
make sure that too much solvent is not used (an issue when using small
volumetric flasks).

Folding a fluted filter paper

To remove solids from a solution, filter through a glass funnel fitted with a fluted
filter paper (increases the rate of filtration). Use the following as a guide to
folding.

Fold in half into quarters than back to half

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Calculations of yields

Percentage yield of product is defined by:


actualyield 100
Percentage yield = ×
theoretical yield 1

The actual yield simply means the amount of purified product as weighed in the
laboratory. The theoretical yield is the maximum possible yield of product as
calculated based on the limiting reactant. Calculation of theoretical yield relies
simply on the laws of proportion.

Example:
3C6H10 + 2KMnO4 + 4H2O → 3C6H10(OH)2 + 2KOH + 2MnO2

2 × 158.03 g produces 3 × 116.16 g (using molecular masses) hence 10.0 g


produces x g in the same proportion or
2 × 158.03 3 × 116.6
=
10.0 x
10.0 × 116.16 × 3
x = = 11.1 g
2 × 158.03

The theoretical yield of C6H10(OH)2 is therefore 11.1 g.

If the actual yield in this case had weighed 2.6 g, then the percentage yield
would have been:
actual yield 100 2.6
percentage yield = × = × 100 = 23%
theoretical yield 1 11.1

When reactants are measured by volume, rather than by weight, the conversion to
weight is required to calculate the number of moles

Even under optimum conditions, the yields of chemical reactions seldom


approach 100%. This is particularly true when the reactants are used in
stoichiometric amounts. Often, a cheap reactant is added in excess to provide for
more effective utilisation of an expensive reactant by driving a reversible
equilibrium toward completion. To increase the purity of a product, one is often
forced to accept a decrease in yield. Usually, a compromise is made between a
maximum yield of rather impure product and a much poorer yield of extremely
pure material.

The art of the synthetic chemist lies in obtaining the highest possible yields of
pure products with the minimum of effort. Although the percent yield is a
criterion for efficiency in the laboratory, it is only one measure among several.
The cost of materials and special equipment must be calculated. Time is perhaps
the most precious commodity of all. Full realisation of the factors making for
success in the laboratory can only come with experience.

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Procedure

A. Copper(II) hydroxide† from copper(II) chloride†

After you have been shown how to use an analytical balance, use it to weigh out,
in a 20-30 mL beaker, between 0.16 g and 0.18 g of CuCl2.2H2O† to 0.001 g.
Record the mass. Add approximately 10 mL of deionised water and stir to
dissolve. Write an ionic equation for this dissolution.

Carefully add, in small amounts with stirring, about 1 mL 5M NaOH† solution.


Any solid which forms is copper(II) hydroxide, Cu(OH)2†. Record your
observations and write a net ionic equation for any change.

To ensure that reaction is complete there must be an excess of NaOH† added to


the solution. The presence of excess OH– ions can be tested for by using litmus
paper which turns blue in basic solutions (solutions containing excess OH– ions).
Test your solution with litmus paper and if the solution is not basic add more
NaOH† solution until it is so.

B. Copper(II) oxide† from copper(II) hydroxide†

Using a bunsen burner, tripod and gauze, gently boil the contents of the beaker for
about 3-5 minutes while stirring constantly to prevent ‘bumping’ of the solution.
Any chemical change that occurs is the removal of a water molecule from
Cu(OH)2† to give copper(II) oxide, CuO†. Record your observations and write a
net ionic equation for any change.

C. Copper(II) sulfate† solution from copper(II) oxide†

Allow the precipitate to settle and carefully decant most of the supernatant
solution through a fluted filter paper. Then transfer the remaining solution and all
the solid to the filter paper. Using a washbottle rinse the beaker with deionised
water into the filter paper. Wash the precipitate on the filter paper with deionised
water and discard all the filtrate.

Place a clean, not necessarily dry, 20-30 mL beaker under the filter funnel, pierce
a small hole in the base of the filter paper with a pasteur pipette and wash the
precipitate through the hole with 3 mL of 5 M H2SO4† (sulfuric acid). If any solid
remains on the filter paper, wash it through with the filtrate (use a pasteur pipette).
When all solid dissolved, wash the filter paper with a little water (keep the filtrate
volume as low as possible). Record your observations and write a net ionic
equation.

__________________________
† See MSDS

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Laboratory Manual

D. Copper from copper(II) sulfate† solution

Do not commence this section unless it can be completed in the time available.

To the coloured solution carefully add, in very small portions, approximately


0.2 g Zn (zinc dust)†. Allow the beaker to stand, stirring occasionally until the
solution becomes colourless. If the solution is not completely colourless, add a
little more Zn† until it is so. Record all your observations and write an ionic
equation.

Wash the precipitate twice by decantation. To do this, allow the precipitate to


settle and decant (pour off) most of the supernatant solution (solution above the
precipitate). Then use a pasteur pipette to remove the last of the water. Add
approximately 10 mL water, swirl the contents, allow the precipitate to settle and
decant the supernate. Repeat with a further 10 mL water. Add 1 mL 5M HCl†
(hydrochloric acid) to the solid and stir. Record your observations. You may or
may not observe a reaction here. If you do, write an ionic equation. If you do not,
explain why HCl† was added to the solid.

(Hint: Zinc† reacts with hydrochloric acid† to evolve H2† (hydrogen gas) but
copper does not.)

Wash the precipitate with deionised water twice by decantation.

E. Calculation of percent yield

Using the analytical balance weigh a clean dry evaporating dish. Record the
mass. Transfer all the copper metal you have prepared to the evaporating dish
using small jets of water from the washbottle. Decant most of the water from the
evaporating dish and heat the dish on a steam bath until it appears dry. Place the
dish in the 100ºC oven for 10 minutes to remove any remaining water and allow
the dish to cool.

Weigh the dish plus the copper and record the mass. Complete the calculations on
the result sheet. Submit your copper sample to your demonstrator for inspection.

__________________________
† See MSDS

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Experiment 4: Classification of matter

Outline

Differences in their behaviour are used to classify compounds into useful


categories. Selected properties of particular categories are examined. The
experiment is of three parts:

A. Conductivity tests are used to classify compounds as electrolytes or non-


electrolytes and inferences are made about bond-type in the tested
substances.

B. The water-solubility of some ionic compounds is examined to confirm


established solubility rules.

C. The action of acid on metal carbonates, oxides and hydroxides is examined.

Objectives

On successfully completing this experiment you should be able to:

• define the terms: element, compound, covalent bond, ionic bond, cation,
anion, electrolyte, acid, base, carbonate, oxide, hydroxide;

• understand that movement of ions is responsible for flow of current through


an electrolyte;

• understand the term dissociation as applied to electrolytes and be able to use


it to explain the difference between strong and weak acids;

• explain why hydrogen chloride in water is an electrolyte but in toluene it is


a non-electrolyte;

• explain how it is possible for an ionic solid, to give a solution of low


conductivity;

• describe the common cations and anions given in this experiment;

• apply the solubility rules given in this experiment;

• understand the action of acid on metal carbonates, oxides and hydroxides;

• write net ionic equations.

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Laboratory Manual

A. Conductivity and electrolytes

Discussion
Part A only will be conducted as a demonstration. Before the demonstration, you
should read the following topics in the Study Guides: classification of matter,
nomenclature and equations, atomic theory and bonding.

Types of bonds in compounds


The bonding between the nuclei in a compound varies from where the electrons
comprising the bond are essentially equally shared by the nuclei, e.g., the C- - -H
bond in methane, CH4, to where the bonding electrons essentially reside on the
one atom, e.g., the Na - - - Cl bond in sodium chloride NaCl.

When the bonding electrons are equally shared we say the bond is a covalent
bond and the compound is made up of essentially neutral (uncharged) molecules,
e.g. methane comprises uncharged molecules of CH4 i.e. molecules of four
hydrogen atoms covalently bonded to one carbon atom. We sometimes depict a
molecule of methane as:
H

H C H

where each dash represents a pair of shared, bonding electrons.

When the electrons essentially reside on the one atom, the solid compound exists
as a regular array of positively and negatively charged species which strongly
attract one another. This attraction (bond) is called an ionic bond since we call
the charged species, ions. Positively charged ions are called cations. Negatively
charged ions are called anions.

For example, table salt, sodium chloride, NaCl, is an ionic solid which consists of
a regular array of Na+ cations and Cl– anions, i.e. the sodium atom has lost an
electron and the chlorine atom has gained an electron.

The term electronegativity is used to describe the attraction by atoms for the
electrons forming bonds between them. Covalent bonds form between atoms of
equal electronegativity. When differences in electronegativity between two atoms
is great, the bond formed between them is ionic, the atom with the higher
electronegativity becoming the anion e.g. Cl has a much higher electronegativity
than Na.

Covalent and ionic bonds are two extremes on a continuum. When


electronegativity differences are intermediate, we obtain polar covalent bonds
i.e. covalent bonds in which the bonding electrons are shared, but unequally e.g.
in hydrogen chloride HCl, chlorine has the higher electronegativity and so the
electrons spend more time near the chlorine atom. We can depict a molecule of
HCl as -

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Laboratory Manual

δ+ δ−
H Cl
H : Cl or H – Cl or

The δ s are partial electronic charges and the shaded area represents the region
where the bonding electrons spend most of their time.

Covalent compounds

Consider a solid covalent compound. This consists of many neutral molecules


packed together. If we heat the solid until it melts we supply enough energy for
the neutral molecules to slide over one another. The solid and liquid are
represented in the diagrams below.
Covalent compound

Solid Liquid

If we dissolve a covalent compound in a liquid, either of two effects, or both, can


occur.
i. the solvent (dissolving liquid) (represented as dark ovals in the figures
below) surrounds the neutral molecules and separates them from each other;
ii. the solvent attracts the molecules of the compound so strongly that the
covalent bonds of the molecules are broken forming cations and anions. We
say the molecules of the compound have dissociated into ions. These two
effects are represented diagrammatically below.

Dissolving a covalent compound

i. Simple dissolution ii. Dissolution with dissociation

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Ionic compounds

Consider a solid ionic compound. If we heat the solid until it melts we supply
enough energy for the oppositely charged ions to slide over one another.

Ionic compound

Solid Liquid

Similarly, if we dissolve an ionic compound, the solvent (represented as dark ovals)


surrounds the cations and anions so they are no longer locked into a regular array.

Solvated anions and cations

Electrolytes

We have seen that liquids and solutions can contain essentially none, some, or a
high proportion of the compound as ions and that the extent of ionization can give
an indication of the bond type in the molecules of the compound.

It is known that electric current is carried through a metal wire by movement of


electrons (we shall defer discussion of bonding in metals). It is also found that
current can flow through some liquids and solutions and that the current in this
case is carried by movement of ions. Substances which conduct electricity are
called electrolytes.

In this experiment the conductivity (capacity to carry current) of liquids and


solutions will be measured to verify the presence of ions and to classify
compounds as electrolytes or not and to link these findings with bond type in the
molecules.

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Procedure

The conductivity meter supplied has the electrodes immersed in deionised water.
Test the conductivity of the deionised water by pressing the button and record the
scale reading. To measure the conductivity of other liquids or solutions, immerse
the electrodes to a uniform depth each time, record the meter reading, rinse the
electrodes with deionised water after each test and store them in deionised water.
Avoid handling the electrodes and take care not to contaminate the solutions.

1. Liquids and solutions


Record the conductivity readings of the liquids and solutions listed in the result
section Table 1 on the result sheet and classify each as a strong (S), (~70–100
scale reading), weak (W) (~20–70), very weak (VW) (~10) or non (N)
(~0) electrolyte.

2. Fusion of solids
Test the conductivity of solid and fused
i. magnesium nitrate hexahydrate, Mg(NO3)2.6H2O, and
ii. camphor, C10H16O.
To do this, place about one teaspoonful of the solid in a porcelain crucible on a
clay triangle on a tripod stand. Hold the electrodes with a pair of tongs and
immerse them in the solid. Record the conductivity reading. Heat the solid
carefully with a bunsen burner until a melt is obtained. Immerse the electrodes
again and record the conductivity of the melt.

Magnesium nitrate is water soluble. Clean electrodes and crucible by washing


with water. Camphor is not water soluble. Clean the electrodes by rinsing with a
little acetone and wiping with paper towel. Do not put camphor in the sinks.
Note: Camphor ignites readily. If ignition does occur, using tongs gently place
the crucible lid over the crucible to extinguish the flame.

3. Effect of electrolyte concentration on solution conductivity


i. Immerse the electrodes in deionised water. Using a microspatula, add
successive, very small amounts of sodium chloride solid, dissolving
each addition and noting the conductivity before adding the next.
Record any evident trend.

ii. Add a small quantity of barium sulfate (BaSO4) solid to deionised


water and stir. Test the conductivity of the solution and record.

4. Effect of solvent on ionization

Make sure the electrodes are dry before immersing them in the prepared solution
of hydrogen chloride (HCl) gas in toluene (stored in fume cupboard). Record the
conductivity.

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B. Water solubility of some ionic compounds

Discussion

It is not a simple matter to predict which ionic compounds are soluble and which
are insoluble in water. A knowledge of solubility rules obviates the need for
lengthy calculations and provides a body of factual knowledge by which several
important operations can be performed. Table 2.1 below lists the common
solubility rules.

Compounds formed from the combination of ions have widely differing water
solubilities. The borderline between soluble and insoluble is therefore arbitrary.
Typically:

soluble : solubility at least 0.1M


slightly soluble : solubility between 0.01M and 0.1M
insoluble : solubility less than 0.01M

In this experiment, ionic compounds will be classified as soluble, slightly soluble


or insoluble depending on whether no, a slight, or a considerable precipitate
respectively, forms when two solutions containing appropriate ions are mixed.
For example, consider the mixing of A, a solution of barium chloride, BaCl2, and
B, a solution of copper(II) sulfate, CuSO4. Both BaCl2 and CuSO4 are soluble so
A contains the ions Ba2+ and Cl– and B contains the ions Cu2+ and SO 24− . When
mixed, all four ions are present together. i.e.

Barium sulfate, BaSO4, is insoluble so these two ions combine and precipitate out
of solution.

Copper (II) chloride, CuCl2, is soluble so does not precipitate out of solution. A
reaction has occurred so we can write an equation. We could write

BaC12(aq ) + CuSO 4(aq ) → BaSO 4(s ) + CuC12(aq )

However if we look more closely at the reacting species and the products we see
that ions were involved. This leads to the idea of a net ionic equation.

We started with Ba (2aq+ ) + 2C1(−aq ) + Cu (2aq+ ) + SO 42−(aq ) and we obtained

BaSO 4(s ) + Cu (2aq+ ) + 2C1(−aq ) . No change occurred with the Cu (2aq+ ) or 2 C1(−aq ) ions.

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Laboratory Manual

These ions are called spectators, they took no part in the reaction. The net
overall reaction was the precipitation of barium sulfate from solution. The net
ionic equation is therefore
Ba (2aq+ ) + SO 42−(aq ) → BaSO 4(s )

Procedure

You are supplied with a series of sodium solutions and a series of nitrate
solutions.

On the surface supplied (previously rinsed with deionised water and dried), add
approximately 1 drop of the appropriate sodium solution, then 1 drop of the
appropriate nitrate solution to confirm the water solubility of each of the
compounds listed in the results section Table 2. Write net ionic equations where
appropriate.

Table 2.1: Common solubility rules

2+
Acetates: : soluble, except Ag+, Hg2 slightly soluble
2+
Bromides: : soluble except Ag+ , Hg2 and Hg2+ and Pb2+ (slightly)
2+
Chlorides: : soluble except Ag+, Hg2 and Pb2+ (slightly)
2+
Iodides: : soluble except Ag+, Hg2 and Hg2+, Pb2+.

Nitrates: : all soluble


2+
Sulfates: : soluble except Sr2+, Ba2+, Hg2 , Pb2+.
Ca2+ and Ag+ slightly soluble
+
Carbonates: : insoluble except Na+, K+, and NH
4
+
Hydroxides: : insoluble except Na+, K+, NH and Ba2+.
4
Ca2+ and Sr2+ slightly soluble
Oxalates: insoluble except Na+, K+.
:
+
NH slightly soluble
4
+
Phosphates: : insoluble except Na+, K+ and NH
4
+
Sulfides: : insoluble except, NH , Group I (Li group)
4
and Group 2 (Be group)
+
Sulfites: : insoluble except Na+, K+ and NH and Mg2+
4

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C. Action of acid on carbonates, oxides and hydroxides

Discussion

( )
Practically all metal carbonates CO 32− , oxides (O2-) and hydroxides (OH–) are
insoluble in water. However they all dissolve when treated with acids (H+). The
generalised ionic equations for divalent metal ions (M2+) can be written as:

MCO 3(s ) + 2H (+aq ) → M (2aq+ ) + CO 2(g ) + H 2 O (l )

MO (s ) + 2H (+aq ) → M (2aq+ ) + H 2 O (l )

M (OH )2(s ) + 2H (+aq ) → M (2aq+ ) + 2H 2 O (l )

Procedure

i. Carbonates

To approximately 1 mL water in a test tube add approximately 0.1 g calcium


carbonate, CaCO3, and shake. Carefully add 6M hydrochloric acid dropwise until
reaction ceases. Record your observations and write an ionic equation for the
reaction.

ii. Oxides

To approximately 1 mL water in a test tube add approximately 0.1 g copper(II)


oxide, CuO, and shake. Add 6M hydrochloric acid dropwise until no further
reaction is observed. Record your observations and write an ionic equation for
the reaction.

iii. Hydroxides

To approximately 1 mL 0.1M iron(III) nitrate solution, Fe(NO 3 )3(aq ) , add 2 mL


0.1M sodium hydroxide solution, NaOH (aq ) . If no change occurs, consult your
demonstrator. Record your observations and write an ionic equation for the
reaction. To the mixture add dropwise with shaking, 6M hydrochloric acid,
HC1(aq ) . Record your observations and write an ionic equation for the reaction.

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Laboratory Manual

Experiment 5: Chemical equilibria

Outline
This experiment involves imposing various changes to chemical systems at
equilibrium, and applying Le Chatelier’s Principle to predict and explain the shift
in the chemical equilibria that these changes cause.

Objectives
• To study some examples of chemical equilibria qualitatively.
• To use Le Chatelier’s Principle to explain what happens when a system at
equilibrium is subjected to a change.

Discussion
Le Chatelier’s Principle tells us that, if a system at equilibrium is subjected to a
change, processes occur that tend to neutralise the imposed change. This enables
us to explain (or even to predict) what happens when we cause a change in the
concentration of a reactant (or product) which is present in chemical equilibrium
with other reactants and products.

You may have already studied the reaction between silver ions, Ag+, and chloride
ions, Cl–. When you finished mixing these reactants in a test tube, you had an
‘equilibrium system’.

Ag+(aq) + Cl–(aq) AgCl(s)

This equilibrium could equally well be written as

AgCl(s) Ag+(aq) + Cl–(aq)

We might need to explain what would happen if some Ag+(aq) were somehow
removed from the solution (i.e. the imposed change is that [Ag+] has been
decreased). Le Chatelier’s Principle helps us to do this (i.e. predict or explain the
change).

If we look at the second equation, Le Chatelier’s Principle tells us the following: a


decrease in [Ag+] will favour the reaction which increases [Ag+], so the forward
reaction will be favoured. When a new equilibrium has been attained (i.e. the
forward and reverse rates are again equal) some AgCl(s) will have dissolved.
Thus the [Cl–] will have increased, and the original decrease in [Ag+] will have
partially counteracted.

For this example we can say that the position of equilibrium has been shifted (or
changed) to the right (i.e. more product, less reactant present). Other equilibrium
systems can be dealt with in a similar manner.

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Laboratory Manual

Procedure

In the following experiments, shifts in equilibria are detected by changes in


colour, etc. Some of these changes are not dramatic, and they are more easily
detected if a portion of the original system/solution is retained for comparison.

1. Silver chloride solubility equilibrium

We can test the effect of removing Ag+ from the silver chloride equilibrium
mixture by adding potassium thiocyanate, KSCN†. This gives a high
concentration of the thiocyanate ion, SCN–, which reacts with Ag+ to give the
soluble complex silver thiocyanate ion, [Ag(SCN)2]–, as follows:

Ag + (aq ) + 2SCN − (aq ) → [Ag(SCN )2]



(aq )

The silver thiocyanate ion, [Ag(SCN)2]–(aq), is quite soluble, and its formation
reaction has a very large equilibrium constant, i.e. it is formed easily.
a. Prepare the silver chloride equilibrium system by mixing small (~1 mL),
equal volumes of 0.2M AgNO3† and 0.2M NaCl† in a test tube.
b. Very slowly add 4M KSCN† solution until you can see that some of the
AgCl(s)† has dissolved. Shake the tube. Now we have a new equilibrium.
c. What happens if more thiocyanate ions are added? Explain why this
happens.

2. Dichromate – chromate ionic equilibrium

a. Balance this equation for the equilibrium between the dichromate and
chromate complex ions.
Cr2O72–(aq) + H2O CrO42–(aq) + H+(aq)

b. Observe the two solutions (Cr2O72–(aq) and CrO42–(aq)) and record their
colours below your equation (on the results sheet).
c. i. Test what happens if you increase [H+]. Do this by adding 2M HCl†
drop by drop to ~ 1 mL of 0.1M K2CrO4† until the colour is noticeably
changed. Record your observations.
ii. Use Le Chatelier’s Principle to explain these observations.
d. i. Test what happens if you increase [OH–]. Do this by adding 2M
KOH† drop by drop to about 1 mL of 0.1M K2Cr2O7.
ii. Record and explain these observations (Le Chatelier’s Principle).
Note: Increasing [OH–] decreases [H+] by reaction to form H2O.
e. Write an equation for the reaction by which OH–(aq) removes H+(aq).

__________________________
† See MSDS

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Laboratory Manual

3. Potassium nitrate solubility equilibrium

This is an example to remind you that the position of equilibrium is generally


changed by changing the temperature. Note that in all other experiments we have
used ‘constant temperature’.
H2O
KNO3(s) + heat energy K+(aq) + NO3–(aq)

a. We can test the effect of heat on the potassium nitrate equilibrium as


follows:
i. Prepare a saturated solution of KNO3† by adding 3g KNO3† (use top
loading balance) to 2.0 mL H2O (use graduated pipette) in a test tube
ii. Heat the mixture to near its boiling point
iii. Record your observations
iv. Explain your observations (Le Chatelier’s Principle).

b. We can test the effect of removing heat from the KNO3† equilibrium system
by allowing the hot solution to cool.
i. Put the test tube in a rack to cool
ii. Record your observations
iii. Observe the shape of the crystals formed.

4. Tetraamine copper(II) complex ion, [Cu(NH3)4]2+(aq).

Cu2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq).


pale blue intense blue
Form the complex ion by adding 1 drop of 0.5M CuCl2† to about 5 mL of
diluted NH3† solution.
a. Test what happens to this equilibrium when [Cu2+] is increased as follows:
Gradually add solid copper sulfate (shaking to dissolve) until you get an
observable result.
b. NH3† can be removed from the system by adding H+(aq) ions
i.e. NH3(aq) + H+(aq) NH4+(aq).
i. Test what happens to the equilibrium when [NH3] is decreased:
Prepare a fresh portion of the complex ion similar to above (i.e. add 5
drops of 0.5M CuCl2† to about 5 mL of dilute NH3† solution) and add
2M HCl† dropwise until there is an observable change. Record your
observations and explain them by using Le Chatelier’s Principle.
ii. What happens when excess HCl† is added?

__________________________
† See MSDS

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Laboratory Manual

c. i. Prepare a solution by adding one drop of 0.5 M CuCl2† to about 5 mL


of 1.0M NH4Cl† solution.

ii. Record your observations (Note: the concentration of the NH3(aq) is


very small). Explain why the solution is almost colourless.

iii. Use Le Chatelier’s Principle to predict what will happen if [NH3] is


increased.

iv. Test your prediction using 2M KOH† to convert NH4+(aq) to NH3(aq)†.


i.e. NH4+(aq) + OH–(aq) ΝΗ3(aq) + H2O(l)
Record your observations.

__________________________
† See MSDS

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Laboratory Manual

Experiment 6: Acid-base equilibria in aqueous


solutions

Outline

The effect of various equilibria on the pH of aqueous solutions is examined. The


experiment is of three parts: A. Hydrolysis of ions. The reactions of dissolved
ions with water, producing pH changes in the solution, are examined; B. Buffer
solutions. Two buffer solutions, of different capacity, are prepared and their
resistance to change in pH is compared with that of pure water; C. Titration
curves and acid-base indicators. Using a pH meter, the pH of solution is
measured during an acid-base titration to plot a titration curve for
• a strong acid/strong base
• a weak acid/strong base, and
• a strong acid/weak base titration.
From the curves obtained, the equivalence point of each titration is determined,
suitable indicators are chosen and the pKA values of two weak acids are found.

Objectives
On completing this experiment you should be able to:

• understand the meaning of a conjugate acid-base pair;


• define the strength of an acid;
• perform a variety of pH calculations;
• explain what a buffer solution is and be able to prepare one of given pH;
• define the term, buffer capacity;
• use a simple pH meter;
• recognise the characteristic shapes of titration curves for:
i. strong acid – strong base
ii. weak acid – strong base
iii. strong acid – weak base titrations
• use titration curves to determine equivalence points and KA values;
• understand why the pH at the equivalence point of an acid-base titration is
generally not 7;
• understand the nature of acid-base indicators;
• choose an appropriate indicator for a particular acid-base titration so that the
end point coincides with the equivalence point.

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Laboratory Manual

Discussion

Part C of this experiment will be conducted as a demonstration during lecture


time. The post-work for Part C should be completed and remains an assessable
part of your laboratory work. Parts A and B will be completed in the laboratory.
You should review the notes in the Modules on pH, pOH and pKa, hydrolysis of
ions, buffer solutions and acid-base titrations.

Hydrolysis of ions

The reactions of ions with water are explored by monitoring the pH of solutions
formed when a range of salts are dissolved. Hydrolysis is a reaction with water
whereby water is cleaved. Depending upon the reaction, the resulting solution
contain OH-(aq) or H3O+(aq). For example, sodium phosphate creates a basic
solution in water.
Dissolution) Na3PO4 (s) → 3Na+(aq) + PO43-(aq)
Hydrolysis of ions Na+(aq) + H2O(l) → no reaction
PO43-(aq) + H2O(l) → HPO42-(aq) + OH-(aq)

Buffer solutions

A buffer solution is a solution which shows little change in pH on addition of


moderate amounts of strong acid or base. A buffer solution contains relatively
high concentrations of a weak acid and its conjugate base.

i.e. HA + H2O A– + H3O+


high concentration high concentration

Addition of a small amount of H3O+ to the solution causes the above equilibrium
to shift towards reactants, increasing [HA] and decreasing [A–]. However, since
these two components are initially present in high concentrations, the relative
change in concentrations is quite small.

The pH of a buffer solution is described by the equation: pH = pK A + log


[A− ]
[HA]
Hence, after addition of a small amount of H3O+, the solution pH is essentially
unchanged. Similarly, with the addition of a small amount of OH–, the solution
pH changes very little. Addition of OH– leads to the reaction
HA + OH- → A– + H2O
The equilibrium then shifts in response to the decreased [HA] and increased [A–].

The capacity of a buffer is a measure of the ability of a buffer to resist changes in


pH.

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Acid-base titrations and titration curves

The purpose of an acid-base titration is to determine the concentration of an


unknown aliquot of a base (or acid) by reacting it with a measured volume of an
acid (or base) of known concentration. Titration curves are graphical
representations of the variation in pH during an acid-base titration as the amount
of titrant is increased.

In this experiment we shall examine the significant features of examples of three


fundamental titrations:

1. Strong acid – strong base: HCl(aq) with NaOH(aq)


At the equivalence point we have a solution of NaCl(aq).
Since neither Na+ nor Cl– has any effect on the pH, the pH at the
equivalence point is 7.00.

2. Strong acid – weak base: HCl(aq) with NH3(aq).


At the equivalence point we have a solution of NH4Cl(aq).
Cl– has no effect on the pH but NH4+ is a weak acid. The pH at the
equivalence point is therefore less than 7.

3. Weak acid – strong base: CH3COOH(aq) with NaOH(aq).


At the equivalence point we have a solution of CH3CO2Na(aq). Na+ has no
effect on the pH but CH3CO2– is the conjugate base of the weak acid, acetic
acid, CH3COOH. The acetate ion therefore makes the pH at the equivalence
point greater than 7.

Other significant features of these titration curves will become apparent from the
experiments and the post work.

Acid-base indicators

Acid-base indicators are simply weak acids which have a markedly differently
coloured conjugate base. If we denote the indicator by HInd and suppose HInd is
red and Ind– is yellow, then in aqueous solution we have
HInd + H2O Ind– + H3O+
Red Yellow
In strongly acidic solutions, the indicator will exist predominantly as HInd (red).
In strongly basic solutions, the indicator will exist as predominantly Ind–
(yellow). (Confirm this by applying Le Chatelier principle.)

However, when there are equal concentrations of HInd and Ind–, the solution will
be orange. We have seen this will occur when pH (solution) = pKA(HInd). In a
titration, if so little of an indicator is used that the pH of the solution is governed
by the acid-base titration itself, the end point (colour change) will be observed
when the pH equals the pKA of the indicator. For a particular titration, a suitable

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indicator is one whose pKA approximately equals the pH of the solution at the
equivalence point.

Note: Because the eye can detect hues of a particular colour, an indicator has a
useful pH range of approximately ± 1 pH unit about its pKA.

The direction of the colour change is also important. It is easier to see the change
from colourless → pink (base added to acid using phenolphthalein) than pink →
colourless (acid added to base).

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Procedure

A. Hydrolysis of ions
1. Thoroughly clean 12 small test tubes and rinse them finally with deionised
water. Set them up in a test tube rack.
2. Add about 2 mL of the supplied, deionised water to each of the test tubes.
3. To each of the test tubes add 1 drop of ‘universal indicator’.
(Note: Universal indicator is a mixture of different indicators which give
colour changes over the pH range 4 to 11.
4. Check that the colour is the same in all the test tubes and by reference to the
colour chart, that the pH of the water is 7. If any tests tubes are
contaminated, discard their contents, clean them again and repeat steps 2
and 3 until all twelve test tubes contain water at pH 7.
5. Keep the first tube as reference and to separate tubes add a small amount
(a few crystals) of each of the salts listed in Table 6.1 on the result sheet.
6. Agitate each tube gently to dissolve the salt and record the pH of the
solution from the colour of the indicator.

B. Buffer solutions
1. Set up ten clean test tubes in a test tube rack and label them 1 to 10.
2. You are supplied with solution A: a solution which is 0.315 M with respect
to HPO 24− † and 0.50 M with respect to H 2 PO −4 †.

3. Accurately dilute 1.00 mL solution A to 10.0 mL to give solution B: a


solution which is 0.0315 M HPO 24− † and 0.050 M H 2 PO −4 †.

4. Into the first four test tubes, transfer, by pasteur pipette, 1.0 mL of
solution A.
5. Into the second four test tubes, transfer 1.0 mL of solution B.
6. Into the remaining two test tubes, transfer 1.0 mL freshly boiled deionised
water.
7. To each of the ten test tubes add one drop of universal indicator.
8. To test tubes 1, 5 and 9 add, 1 drop of 1.0 M HCl.
To test tubes 2, 6 and 10 add, 1 drop of 1.0 M NaOH.
To test tubes 3 and 7 add, 1 drop of 5.0 M HCl.
To test tubes 4 and 8 add, 1 drop of 5.0 M NaOH.
In Table 6.2 on the result sheet record the pH of each solution from the
colour of the indicator.

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C. Titration curves and acid-base indicators

Titration 1

1. Set up the apparatus shown in the sketch below.

100 mL beaker

2. Record the precise concentration of the approximately 1.0 M HCl stock


solution.

3. Using a pipette, transfer 2.00 mL stock NaOH† solution into the clean
100 mL beaker, add 40-50 mL of deionised water and add 2-3 drops of
bromothymol blue indicator. Add just enough water to ensure that the bulb
of the electrode is immersed in the solution, stir the solution gently using
the magnetic follower and record the pH of the solution in Table 6.3 of the
result sheet.

4. Use a little of the supplied HCl† to rinse a burette. Fill this burette to
somewhere near the 0 mL mark and record the reading to the nearest 0.01
mL.

5. Run the acid in from the burette rapidly until the solution becomes slightly
acidic. Record the burette reading.

6. Calculate the volume of acid added in this rough titration. Determine


appropriate volume additions of acid to be made in order to collect roughly
20 data points in the following accurate titration.

7. Repeat the titration using a fresh 2.00 mL aliquot (sample) of the base,
deliver the appropriate volumes of stock HCl† solution and record the pH
and indicator colour after each addition in the corresponding square in Table
6.3 on the result sheet.

8. Discard the solution, rinse and dry the apparatus and reassemble as in step
1.

9. On a sheet of graph paper, plot pH against volume of HCl† added to obtain


a titration curve for NaOH† against HCl†.

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Titration 2

1. Set up the pH meter as in Titration 1.

2. Fill the burette to somewhere near the 0 mL mark with the approx. 1.0 M
hydrochloric acid solution and record the reading to the nearest 0.01 mL.

3. Using a pipette, transfer 2.00 mL stock NH3† solution to the clean 50 mL


beaker, add 1 drop of methyl red indicator, immerse the electrode, stir the
solution and record the pH indicator colour.

4. Run the acid in from the burette rapidly until the solution becomes slightly
acidic. Record the burette reading.

5. Calculate the volume of acid added in this rough titration. Determine


appropriate volume additions of acid to be made in order to collect roughly
20 data points in the following accurate titration.

6. From the burette, deliver the appropriate volumes of stock HCl† solution
and record the pH and the indicator colour after each addition, in the
corresponding square in Table 6.4 on the result sheet.

7. Discard the solution, rinse and dry the apparatus.

8. On a sheet of graph paper, plot pH against volume HCl† added to obtain a


titration curve, for NH3† against HCl†.

Titration 3

The following is a simulated experiment, the data has been supplied in Table 6.5.

1. Using a pipette, transfer 2.00 mL stock CH3COOH† solution to the clean 50


mL beaker, add 1 drop of phenolphthalein indicator, immerse the electrode,
stir the solution and record the pH and the indicator colour in Table 6.5 on
the result sheet.

2. From the (well-rinsed) burette, deliver the appropriate volumes of stock


NaOH† solution and record the pH and the indicator colour after each
addition in the corresponding square in Table 6.5 on the result sheet.

3. Empty the beaker and the burette and rinse all the apparatus, including the
electrode, with tap water. Give the electrode a final rinse with deionised
water.

4. On a sheet of graph paper, plot pH against volume of NaOH† added to


obtain a titration curve for CH3COOH† against NaOH†.

__________________________
† See MSDS

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