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Chemistry Investigation: Volumetric and

Colorimetric Analysis of the copper content


of coins.

Iain Sword
064312723
Elgin Academy

Iain Sword 604312723 Elgin Academy

Page 1

Contents:
Introduction

Aim

Summary

A brief history of the penny

Underlying Chemistry

Dissolving Unreactive Metals

Colorimetric Analysis

Volumetric Analysis

10

Procedures

12

Producing a Copper Nitrate solution from a 1


penny coin
Colorimetric Analysis

12

Volumetric Analysis

18

Discussion

13

20

Conclusion

20

Evaluation

21

Colorimetric Analysis

21

Volumetric Analysis

22

Appendices

22

Uncertainties

23

Preparation of sodium thiosulphate solution

24

Calculation of the required volume of KI solution


References

24
25

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Introduction
Aim:
The aim of this investigation was to compare the techniques of colorimetric and
volumetric analysis for the determination of the copper content of pre 1992 one penny
coins.

Summary
Colorimetric Analysis:
The average percentage of copper by colorimetric analysis was found to be 103.21.5%

Volumetric Analysis:
The average percentage of copper by volumetric analysis was found to be 94.71.2%
Therefore based on royal mint specifications, that copper coins are 97% copper, 2.5%
zinc and 0.5% tin. (royalmint.com)
The volumetric method was both more accurate and precise.

A brief history of the penny


The UK has used pennies as a denomination of currency since 785AD which were initially
produced as an alloy of silver and copper. The weight and composition of these pennies
changed throughout the dark ages and medieval period. With the rule of the Stuart
Dynasty a true copper farthing was introduced which would be more equivalent to a
modern penny. However when the House of Hanover took over rule of England, the silver
penny was phased out gradually being replaced by copper. A the beginning of the 20th
century the composition was standardised at 95.5% copper, 3% tin and 1.5% zinc. This
composition remained until the Second World War when the tin composition was
decreased and copper was increased due to a national tin shortage. The old composition
was restored at the conclusion of the war. The minting of pennies was ceased during the
1950s, but when it resumed in 1962 the composition used during the Second World War
(97% Cu, 0.5% Sn, 2.5% Zn) continued to be used to the present day as a decimalised
currency since 1970

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Underlying Chemistry
Dissolving an unreactive metal
Though nitric acid generally behaves like other dilute acids at lower concentrations (0.11mol.l-1) it can exhibit qualities not shown by other acids as its concentration is
increased. These are thought to be due to the increased concentration of the nitrate ion.
When using a very dilute acid such as nitric acid (0.1 mol.l -1), the primary reaction taking
place when the acid is added to a metal is:

METAL+ ACID SALT + HYDROGEN

( aq ) Mg (N O3 )2 + H 2 (g)
+ N O3
Mg ( s )+ 2 H
Where the hydrogen ions are reduced by the metals, releasing hydrogen gas. However
this reaction will only occur with particularly reactive metals (i.e. above hydrogen in the
electrochemical series) such as magnesium and zinc. This is because the overall change
in free energy in a reaction must always be negative. The free energy in a reaction can
where G
is the change in free
G=nF E0
energy for the reaction n
is the number of electrons used in the redox step, F
be defined by

is faraday's constant (the charge carried by one mole of electrons, 9.65x10 4C) and

E0

is the overall reduction potential for the equation.


For the example of copper, the overall for

H 2
++2 e
2 H
Cu

2++2 e

Cu

is positive,

E0=0.00V
E0=0.34 V

2+ + H 2
So the overall reduction potential for the redox + Cu is the difference between
Cu+ 2 H
that of the two relevant half equations: E0=0.000.34=0.34 V
4
G=29.6510 0.3 4
3
G=65.6210 J
so the action is thermodynamically unfeasible. Whereas the G value for magnesium
is negative, indicating the reaction is thermodynamically feasible.

H 2
++2 e
2 H
Mg

2+ +2 e
Mg

E0=0.00V
E0=2.37 V

2+ + H 2
So the overall reduction potential for the redox + Mg is the difference between
Mg+2 H
that of the two relevant half equations: E0=0.00(2.37)=2.37 V
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G=29.6510 2.37
3
G=457.410 J

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If the concentration of nitric acid is increased up to approximately 1-2 mol.l -1 then a


different equation is produced.

2+( aq)+ 2 NO ( g ) + 4 H 2 O(l)


+ 3Cu
( aq ) +8 H
3 Cu ( s ) +2 N O3
In this reaction the Nitric Oxide species is evolved. In addition this reaction is not limited
to those above hydrogen on the electrochemical series
When concentrated nitric acid is used however, a different reaction is again produced:

2+( aq)+ 2 NO ( g ) +2 H 2 O(l)


+ Cu
( aq ) +4 H
Cu ( s ) +2 N O 3
This was the reaction used to dissolve the coins for the further experiments. It had to be
performed in a fume cupboard as large volumes of the highly toxic nitrogen dioxide
species were evolved.
(Garvie, Reid & Robertson, 1976)

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Here are two examples of Conc. Nitric acid dissolving copper coins, producing brown
nitrogen dioxide. The green beaker on the left has nearly finished reacting as the volume
of gas produced has decreased substantially. The beaker on the right however has only
just started reacting, shown by the large volume of brown gas in the
beaker.Colorimetric

Analysis

Colorimetric determination relies on the substance under test absorbing certain


wavelengths of light while transmitting others. Solutions of copper (II) ions transmit
primarily in the cyan region of the EM spectrum as they have a pale blue/cyan colour.
This corresponds to them absorbing strongly in the red region. This was also confirmed
by experiment using the different filters in the colorimeter.

Yello
w

Gree
n
Cyan

Red

Magent
a
Blue

(blog.asmartbear.com)
From the colour wheel above, you can see that if a substance absorbs primarily in one
region, the region opposite will be the colour the solution appears. For example a solution
that appears yellow will do so because it absorbs strongly in the blue region of the
spectrum leaving only yellow regions to pass through.

Colour
absorbed

Colour
observed

Blue

Yellow

Green

Magenta

Red

Cyan

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When the copper 2+ ions are dissolved in water the water molecules form ligands around
the copper ions. A ligand is a molecule or negative ion with at least one lone pair of
electrons that is attracted to an ion (examples being water, ammonia, EDTA and oxalate
ions). (chemwiki.ucdavis.edu)

6 water ligands formed an octahedral arrangement around a central atom or ion.


The - oxygen ion with its lone pairs is attracted towards the central ion or atom
All electrons exist in energy levels. These can be further divided into subshells which are
further separated into orbitals.
In free transition metal atoms and ions, the ions have a 3d subshell which is subdivided
into 5 degenerate orbitals (i.e. they all have the same energy).

(home.freeuk.net)

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When in an octahedral complex [Cu(H2O)6]2+, the water ligands will approach the copper
ion along the x, y and z axes and repel the electrons in the orbitals oriented along these
axes (dx2-y2 and dz2) and so have a higher energy. This leads to a loss of degeneracy in the
d orbitals with the dxy, dxz and dyz orbitals having a lower energy. Due to this loss of
degeneracy, when light passes though the solution, light of wavelengths able to excite
electrons causing them to jump from the lower d orbitals to higher d orbitals will be
absorbed causing the solution to appear coloured. This appearence of colour is due to the
energy of photons absorbed corresponding to the wavelength by the equation

E=

Lhc

(6.02*1023),

where

is the energy of the photon,

is Planck's constant (6.63*10-34),

L is avagadro's constant
is the speed of light (3*108) and

is the wavelength of light absorbed

Energy

large energy difference


small difference in energy

degenerate d orbitals in "free" ion


d orbitals split by a "weak field" ligand such as Id orbitals split by a "strong field" ligand such as CN-

Diagram from (Gibb & Hawley, 2010)


The strength of these ligands is determined from the spectrochemical series:
CN->NH3>H2O>OH->F->Cl->Br->I-

Each of these copper chloride solutions has increasing volumes of aqueous ammonia
solution (left to right). The change in the colour of light transmitted is because the size of
the d-d transition increases due to ammonia being higher in the spectrochemical series
than water.
(dwb.unl.edu)
E.g for copper

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Iain Sword 604312723 Elgin Academy

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To analyse compounds by colorimetry, one must use a colorimeter. They operate by using
a light source to shine a beam of light through a sample contained in a cuvette. The light
transmitted through the cuvette then hits a light sensor (likely a photoresistor) which
measures the light transmitted. Before running the sensor on the desired sample, a
reference sample must also be tested to set a baseline absorbance for the cuvette. This
reference cuvette is commonly filled with deionised water.

Simplified Colorimeter diagram


(docbrown.info)
To determine the absorbance of the sample, the colorimeter calculates a value based on
the beer-lambert law. By this law, the absorbance of a solution can be expressed as

A=ln

( II )
0

and

I0

where

ln

represents the natural log function;

are the intensities of transmitted and incident radiation respectively where

intensity is measured in power per unit area (Wcm-2)


Because A Conc it is possible to create a standard curve by plotting known values
for concentration (by making standard solutions of Cu(NO3)2 ) against absorbance and
comparing the curve with absorbance values from the prepared samples from the penny
coins which will contain Cu2+ ions from their reaction with nitric acid (pg5)

Abs.

[Cu2+]

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Volumetric Analysis
To analyse the copper content of copper nitrate solutions produced from coins by
Volumetric Analysis, the solution must first be converted into a different set of
compounds that will react with an indicator to produce a colour change. To do this any
excess nitric acid first had to be neutralised. The reason for this is because a side
reaction occurs between excess nitric acid and the sodium thiosulphate used in the
titration (this would decrease the yield of

ions and move the reactions end

point).

Na2 S2 O3+2 HN O3 2 NaN O3 + S O2+ S + H 2 O

To deal with excess acid, it can be reacted with a metal carbonate, such as calcium or
sodium producing the following reaction:

HN O3 + Na 2 C O3 2 NaN O3 +C O2 + H 2 O
To determine the concentration of Cu(II) ions by titration an iodide salt such as potassium
iodide can be reacted with the copper ions where copper (II) ions are reduced to copper
(I) by iodides as it oxidises to elemental iodine however this is unusual as the reduction

2I
potential for
I 2+2 e

Cu
(E0=0.54 V) is higher than that of
2+ +e

Cu

( E0=0.17 V). However, because copper iodide produced in the reaction is very insoluble
creating very low concentrations of copper iodide and because reduction potentials are
measured at 1mol.l-1 this value is inaccurate and in reality is closer to 0.88V causing the
reaction go as observed.

N O3

2+

2 Cu

Sodium thiosulphate can be reacted with iodine produced in the above reaction:

+ Na2 S 4 O6
I 2 +2 Na2 S2 O 3 2 I
So the overall equation for the reaction can be thought of as:

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N O3

2+

2 Cu
This gives a ratio between the reaction components of:

2
2+ : I 2 :S 2 O3
Cu
2: 1 :2
This ratio allows the number of moles of copper ions to be determined from the number
of moles of thiosulphate ions directly as the ratio between the two is 1:1.

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I 2 ) solutions have a very strong brown colour while


At high concentrations, iodine (
at lower concentrations such as near the end point the colour is a far more pale yellow
making it difficult to determine the end point. To make this end point easier to detect, a
starch indicator is used as it creates a colour change by creating a blue coloured complex
with

I3

ions through adsorption with

I3

ions being formed by the reaction

I 3 . This reaction is highly reversible at low concentrations however at higher


I 2+ I
concentrations the bonding between starch and iodine ions becomes much stronger and
slows down the adsorption of iodine making end points more difficult to spot. This is a
common occurrence if starch is added early on in the titration when iodine
concentrations are still high.
(titrations.info)
To remove the excess nitric left over from the initial reaction with the coin, it can be
neutralised with an aqueous solution of calcium carbonate, following the reaction below

2 H NO 3+CaC O3 Ca ( N O3 )2+ H 2 O+C O 2


Primary standards are used in analytical chemistry to compare and test other chemicals
as their properties are very well understood and are stable. Producing a very accurate
solution of a primary standard simply requires weighing out a mass and diluting to an
appropriate volume. To meet the criteria of being a primary standard the compound must
meet a set of strict requirements:
Stable in air over long periods
Highly pure and cheap
No water of hydration which could change with atmospheric conditions such as
humidity and temperature
Dissolves readily in a chosen solvent to produce a stable solution
A large molecular mass
Sodium thiosulphate, while satisfying many of these criteria does not qualify as a primary
standard as it exists as a hydrated salt which can change in water content with changing
conditions. Examples of true primary standards include: Anhydrous sodium carbonate,
silver nitrate and potassium hydrogen phthalate. How a solution of sodium thiosulphate
could be standardised is detailed in the evaluation.
(csudh.edu)

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Procedures
Producing a Copper Nitrate solution from a 1
penny coin
The two procedures used for determining the percentage of copper in coins required that
a solution of Copper Nitrate was produced. This same procedure was used in both
methods.
Equipment:

100cm3 glass beakers (pyrex glass)


Fume cupboard
Balance (accurate to 3d.p. or more)
250cm3 volumetric flask

Reagents:

Concentrated nitric acid, 25cm3 per coin


Pre-1992 1 pence copper coins
Deionised water as required

Method:
Approximately 25cm3 of conc nitric acid was poured into a 100cm3 glass beaker using
the beakers marked scale. The beaker was then placed into the fume cupboard as
toxic nitrogen dioxide would be evolved during the reaction. A coin was weighed on a
tared balance and this mass was noted down. This coin was then dropped carefully
into the beaker then the beaker was pushed further into the fume cupboard to
minimise the risk of nitrogen dioxide escaping. The coin/acid solution was then left
until the coin had completely reacted, indicated by no more nitrogen dioxide being
produced and all effervescence ceasing in the beaker. The dark green/blue liquid
remaining was then diluted with deionised water so the energy released by any
excess acid being diluted could be done under controlled conditions in a reinforced
beaker. This partially diluted solution was then poured into a 250cm 3 volumetric flask
and further diluted up to the beginning of the neck of the flask, stoppered, inverted
then left to settle, then filled up to the graduation mark and finally stoppered,
inverted and settled again.

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Colorimetric Analysis
1) Absorption Spectrum
To determine the filter most suited to the experiment an absorption spectrum was
created using a stock solution of copper nitrate (aprox 1 mol.l-1)
To create the curve a colorimeter was used, a sample of copper (II) nitrate and deionised
water were poured into 2 identical cuvettes. The following procedure was repeated for
each filter:
The reference (deionised water) cuvette was inserted into the colorimeter and the
reference point was set to zero. The reference cuvette was removed and replaced with
the test cuvette (copper (II) nitrate) and a reading was taken.

Filter wavelength
(nm)
440
470
490
520
580
590
680

Absorbance (A)
Run 1
Run 2
-0.01
0
0.06
0.23
0.54
1.01
off top of
scale

0.02
0.04
0.06
0.09
0.5
0.91
off top of
scale

1.6
1.4
1.2
1
Absorbance (A)

0.8

Absorbance

0.6

Absorbance run 2

0.4

Exponential
(Absorbance run 2)

0.2
0
-0.2400 500 600 700
Wavelength (nm)

Conclusion
This graph shows that with the filters that were available, the filter that would give the
greatest absorbance would be filter allowing 680nm (red) light to pass through. So this
was the filter used for all subsequent tests.

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2) Calibration curve
To allow the results of the experiments done with coins to be analysed a series of
calibration curves were created. The procedure for these was as follows:
Equipment:
100cm3 glass beakers (pyrex glass)
Balance (accurate to 3d.p.)
50cm3 volumetric flasks
Colorimeter with 680nm filter
2 Matching Cuvettes
Weighing boats
Reagents:
Solid Copper Nitrate (up to 40g per graph created)
Deionised water as required
Method:
Masses of approximately 1.2g, 2.4g, 3.6g, 4.8g, 6.0g, 7.2g and 8.4g solid copper
nitrate were accurately weighed out on a tared balance in weighing boats. Each of
these masses were poured from the weighing boats used to weigh them out into a
beaker and the weighing boat was rinsed over the beaker with deionised water to
collect all the copper nitrate which was then partially diluted to ease pouring into
volumetric flasks. The concentrated solution of copper nitrate was then poured into a
50cm3 volumetric flask. A cuvette was used filled with deionised water. The cuvette
with deionised water was then inserted into the colorimeter and then a zero value for
absorbance was set. The cuvette was then removed. A matching cuvette was then
filled with the copper nitrate, inserted into the colorimeter and an absorbance value
was taken. The preparation of the cuvette and measurement of absorbance was
repeated 3 times for each value of concentration, and the whole procedure repeated
at each concentration. The whole process was duplicated to produce a second
calibration curve.
Note: care was taken to hold the cuvettes by the opaque sides and insert with the
clear sides along the light path.

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Calibration graph 1
Sample calculation (formula mass for Cu(NO3)2.3H20=241.6g):
n=

m 1.210
=
=0.005 mol
Fm 241.6

C=

1000 n 10000.005
=
=0.1 mol . l1
V
50

Weighed
mass of
copper
nitrate (g)
1.210
2.395
3.617
4.815
6.006
7.265
8.441

Calculated
concentrati
on (mol.l-1)
0.100
0.198
0.299
0.399
0.497
0.601
0.699

Absorbance (A)
Run 1
No data
0.66
0.99
1.29
1.58
1.86
off top of
scale

Run 2

Run 3

0.35
0.66
0.97
1.21
1.51
1.81
off top of
scale

0.29
0.62
0.94
1.23
1.53
1.82
off top of
scale

Average
0.32
0.65
0.97
1.24
1.54
1.83
off top of
scale

Calibration graph 2
Weighed
mass of
copper
nitrate (g)
1.203
2.390
3.577
4.836
6.066
7.242
8.448

Calculated
concentrati
on (mol.l-1)
0.100
0.198
0.296
0.400
0.502
0.600
0.699

Absorbance (A)
Run 1
0.35
0.67
0.97
1.07
1.63
1.90
off top of
scale

Run 2
0.35
0.69
1.13
1.10
1.65
1.97
off top of
scale

Run 3
0.33
0.69
1.00
1.26
1.65
1.98
off top of scale

Average
0.34
0.68
1.03
1.14
1.64
1.95
off top of
scale

Calibration graphs

Iain Sword 604312723 Elgin Academy

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3) Colorimetric determination of copper content of coins


Equipment:

100cm3 glass beakers (pyrex glass)


Colorimeter with 680nm filter
2 Matching Cuvettes

Reagents:

Pre-1992 1 pence coins


Deionised water as required

Method:
Three 1p coins were weighed separately on a tared balance. Then each coin was
placed in a separate beaker containing approximately 25cm3 of concentrated nitric
acid and allowed to react completely (when no more NO 2 fumes were given off). The
solution was then diluted with deionised water and transferred into a 250cm 3
volumetric flask with washings. The flask was then made up to the 250cm3 mark then
stoppered and inverted (this procedure is analogous with that on pg12) A reference
value was set by inserting a cuvette filled with deionized water into the colorimeter
and setting it as the reference value. A small volume of coin/copper nitrate solution
was then poured into a matching cuvette. The cuvette was placed into the
colorimeter and its absorbance was taken. 3 cuvettes were prepared for each
solution. The previous procedure was completed for each coin. The absorbance
results were then inserted into the equations from the calibration curves to produce
concentration values as seen on the table.

Results:
Raw Data:
Coin
no.

Coin
mass
(g)

1
2
3

3.544
3.620
3.510

Coin no.

Run
1
0.91
0.80
0.72

Absorbance (A)
Run
Run
Averag
2
3
e
0.90 0.92 0.91
0.79 0.79 0.79
0.72 0.72 0.72

Using Calibration Curve 1

Using Calibration Curve 2

Concentrati
on (mol.l-1)

Mas
s (g)

%
Coppe
r
Conte
nt

Concentrati
on (mol.l-1)

Mas
s (g)

%
Coppe
r
Conte
nt

0.29

4.58

129

0.28

4.42

125

0.22

3.50

96.5

0.22

3.41

94.1

0.20

3.08

87.9

0.19

3.04

86.5

Iain Sword 604312723 Elgin Academy

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To calculate the % of copper, the following sequence of calculations was used:


1. Concentration was calculated using the average absorbance and the line of best fit
equation from the calibration curve:

Concentration=

Absorbance y intercept
Gradient

2. Number of moles was calculated using


number of moles in a solution, V
the concentration of the solution.
3. Then the mass is calculated using
mass of the solution component,
compound and

V C
1000

where

is the volume of the solution and

is the

is

m=Fmn
where m
is the
Fm
is the relative formula mass of the

is the number of moles in a solution.

4. Finally percentage is calculated by


percentage, m
mass of the coin.

n=

100 m
mcoin

is the mass of copper in the coin and

where

mcoin

is the
is the initial

E.g: coin 1, using calibration graph one:

C=
n=

0.910.0442
=0.29 mol . l1
2.9998

0.29250
=0.073 mol
1000

m=0.07363.5=4.58 g

Cu

4.58
100=129
3.544

To find the mean value for this method, all of the final percentages were used giving
103.21.6%

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Page 21

Volumetric Analysis
Equipment:

100cm3 glass beakers (pyrex glass)


25cm3 bulb pipette
dropper
250cm3 volumetric flask
50cm3 burette
10cm3 measuring cylinder

Reagents:

Deionised water as required


1mol.l-1 calcium carbonate solution 50cm3 per coin
Dilute (1mol.l-1) ethanoic acid (25cm3)
1mol.l-1 potassium iodide solution, 50cm3 per coin
Sodium Thiosulphate solution, 0.22mol.l-1 as required (see appendix 2 for
preparation)
0.2% starch solution, 10cm3 per coin

Method:
Three 1p coins were weighed separately on a tared balance. Then each coin was placed
in a separate beaker containing approximately 25cm3 of concentrated nitric acid and
allowed to react completely (when no more NO2 fumes were given off). The solution was
then diluted with deionised water and transferred into a 250cm3 volumetric flask with
washings. The flask was then made up to the 250cm3 mark then stoppered and inverted
(this procedure is analogous with that on pg12).For each solution 25cm3 was pipetted
into a conical flask this was repeated a further 3 ties to give 4 flasks of Copper(II)Nitrate
solution. A 1 mol.l-1 solution of calcium carbonate was carefully added to each conical
flask until a small mass of precipitate was formed and remained in the flask indicating
any excess nitric acid had been neutralised. A volume of dilute ethanoic acid was then
added to the conical flask until any remaining precipitate had dissolved. 10cm 3 of 1 mol.l1
potassium iodide measured in a 10cm3 measuring cylinder was added to the solution
which produced a colour change from transparent blue to cloudy brown. A fresh solution
of sodium thiosulphate was then produced as the titre. The burette was prepared for
titration by rinsing out with the prepared thiosulphate solution then filling with the same
solution and noting the start point. The titration was then carried out by adding
thiosulphate until the solution becomes very pale then 1cm3 of starch indicator was
added producing a purple/blue colour at the point of contact and turning the solution a
pale pink colour. Small volumes of thiosulphate should continue to be added followed by
drops of starch indicator until no more purple colour is produced. The volume of
thiosulphate required to complete the reaction is then noted from the end point on the
burette. The difference between start and end volumes is the Titre. The titration solution
in conical flask and titration was then repeated as necessary to produce concordant
results. Each set of results was repeated for each coin.

Iain Sword 604312723 Elgin Academy

Page 22

Results:
Coin
No.

Run
no

Start
Vol
(cm3)
0.0

End
Vol
(cm3)
24.0

2
3
4
1

24.0
0.0

48.7
24.7
n/a
48.8

2
3
4
1
2
3
4

0.0
24.9

Coi
n
no.

Mass of
coin (g)

1
2
3

3.611
3.598
3.584

24.8

0.0
23.0
0.0
23.4
Number
of
moles
of
copper
in
25cm3
0.0054
0.0055
0.0052

Titre
(cm3)
23.0>24.0
24.7
24.7

Average
Titre
(cm3)
24.7

23.0>25.0
24.9
25.0

24.95

22->23
22.3
23.4
23.5

23.45

Number
of moles
of
copper
in
250cm3

Mass of
copper
in coin
(g)

%
coppe
r in
coin

0.054
0.055
0.052

3.43
3.49
3.30

95.0
96.9
92.1

24.9
49.9
n/a
23.0
45.3
23.4
46.9

Sample Calculation (coin 1):


As the ratio of Thiosulphate ions to Copper ions is 1:1, nthiosulphate=ncopper

n=

VC 24.70.22
=
=0.0054 mol
1000
1000

this value for n applies to the copper in the 25cm3 pipette, n for the 250cm3 volumetric
flask is 0.054mol as its volume is 10 times that of the pipette.

m=nFM =0.05463.5=3.43 g

Cu

mCu
3.43
100=
=95.0
m coin
3.611

Conclusion
The average percentage of copper in a 1p coin is 94.71.1%

Iain Sword 604312723 Elgin Academy

Page 23

Discussion
Conclusion
Method

Average percentage copper content of


a coin

Colorimetric
Analysis

103.21.6%

Volumetric
Analysis

94.71.1%

When compared with the royal mint value for the percentage of copper in 1 penny coins
of 97% it can be seen that volumetric analysis is both a more accurate and precise
method as it is closer to the expected value and the uncertainty in this value is also
lower.

Iain Sword 604312723 Elgin Academy

Page 24

Evaluation
Dissolving the Coins
Because this procedure is common to both techniques the errors involved can be
disregarded for the purpose of comparison. The errors that could contribute however
which are not covered by the measurement uncertainties are as follows: The coin did not
entirely react with the nitric acid, however this was avoided by adding excess nitric acid
to the beaker. Any splashes from the beaker which could result in lost copper, though
none were observed. Had any of these other errors occurred they would likely have
caused a decrease in the copper in the solution, causing a decrease in the concentration
and a lower result overall for the percentage of copper in the coin.

Colorimetric Analysis
1) The errors involved in determining the maximum absorbance come only from the
colorimeter scale as all other factors were kept constant. The difference between results
was far larger than the inaccuracy in the scale on the colorimeter giving my greater
confidence that the red filter was the correct one to use.
2) The percentage errors in the mass of copper nitrate salt weighed out decreases as the
mass of salt increases. Making it unusual that the lines in the calibration curve begin to
drift apart, however this can be explained by assumptions taken by the graphing
software treating all points equally. The lines are however very close together allowing
me to be confident they are accurate.
3) Though the procedure uncertainty for this was 1.6%, the random uncertainty for the
results was 7.2% suggesting that other errors were present causing the result to err
significantly above the expected value. The possible reasons for this include: The
cuvettes being inserted incorrectly or selecting a non-identical set of cuvettes (both of
which I took care not to do), any contact with greasy fingerprints against the clear sides
of the cuvette (which was possible while removing the cuvettes from the packaging) this
error would cause an increase in the read absorbance value and lead to an increased
value for concentration and final percentage of copper in the coin. This causes me to
believe that it could at least in part be responsible for the overall result being higher than
expected. To remove this error in a future experiment more care could be taken when
handling the cuvettes. The other primary factor that could possibly influence the result
would be interactions by the zinc and tin ions in the solution. These ions have either full
or empty outer d orbitals making d-d transitions unlikely to be the cause for the colour
effect. However permanganate ions are able to produce a strong purple colour despite
having an empty d orbital. The presence of zinc and tin ions may cause the result for
absorbance become higher and in turn lead to an increased result for copper content in
the coin making it probable that it plays a part in producing results that do not conform
to the stated figures. To determine of this uncertainty in future I would create the
calibration curves with a mixture similar to that of a coins composition (97% copper,
2.5% zinc, 0.5% tin).

Iain Sword 604312723 Elgin Academy

Page 25

Iain Sword 604312723 Elgin Academy

Page 26

Volumetric Analysis
The procedure uncertainty for this procedure was 1.1% while the random uncertainty
was 1.4% based on the results. The expected value (97%) however does not fall within
the range generated by either uncertainty from the average result. This suggests that
many other factors were at play that could be not controlled. This could include side
reactions in the conical flask prior to titration (such as excess acid reacting with iodine)
as well as not correctly identifying the end point due to a colour change that was hard to
determine.
When determining the end point it was likely that I pre-empted this, causing a lower
volume of thiosulphate to be recorded and therefore a lower percentage copper
calculated.
Other effects that could influence the result were impurities in the reagents used. For
example the sodium thiosulphate crystals may have been impure causing the expected
concentration to be incorrect. This would have decreased the number of moles in
solution. This would mean that the calculated value should have been lowered further
still.
As sodium thiosulphate is not a primary standard due its variable water content, this
could have either inceased or decreased the concentration of the solution based on
ambient conditions. It would have been possible to verify the concentration of the
solution using the primary standard Potassium Iodate. This was not done during my
experiment due to time constraints and because the thiosulphate solutions were made
up fresh on the day of use from the crystals to minimise any errors that may occur during
storage. The titrations were all carried out in a single afternoon, and so the ambient
conditions were constant. However this error cannot be quantified.
When adding the Potassium iodide used to create the colour, the reaction relies on an
excess volume of KI solution being added to ensure all the copper was reacted. The
actual volume added was not important and so a measuring cylinder could be used. This
solution was added using a 10cm3 measuring cylinder. The minimum volume for this was
calculated, in retrospect, to be 11cm3 on average. So it is very likely that an inadequate
volume of potassium iodide was added to solution leading to a likely source of error.
Therefore the mass of copper would be less than was present.
The major errors in this procedure were in determining the end point and in using
insufficient KI solution, with the use of insufficient KI having the most marked effect on
the results, resulting in a calculated value of copper content being lower than was
actually present.

Iain Sword 604312723 Elgin Academy

Page 27

Appendices:
Appendix 1: Uncertainties
The procedure uncertainties were derived from the valued stated on the equipment and
the specifications stated for class B scientific glassware (jaytecglass.co.uk)

Item

Toleranc
e

3d.p. Weighing
balance

0.001
g

50cm3 volumetric
flask (class B)

0.12c
m3

2d.p. colorimeter

0.01A

250cm3 volumetric
flask (class B)

0.3cm

25cm3 pipette

0.06c
m3

50cm3 burette

0.1cm

Using the values from the table above:

Uncertainty in colorimetric analysis:


Uncertainty in weighing
Uncertainty in 50cm3
volumetric flask
Uncertainty in
absorbance value
Overall uncertainty
Uncertainty in % copper
content

0.001
100=average 0.03
Coin starting masses
0.12
100=0.24
50
0.01
=1 , 1.3 , 1.4
Absorbances
1.27%, 1.57%, 1.67% average 1.50%
1.50% of average copper content =
1.6%

Uncertainty in volumetric analysis:


Uncertainty in weighing
Uncertainty in 250cm3
volumetric flask
Uncertainty in pipette
Uncertainty in burette
readings
Overall uncertainty
Uncertainty in % copper
content

0.001
100=average 0.03
Coin starting masses
0.3
100=0.12
250
0.06
=0.24
25
0.2
100=0.8 , 0.8 , 0.9
titre volumes
1.19%, 1.19%, 1.29% average 1.22%
1.22% of average copper content =
1.1%

Iain Sword 604312723 Elgin Academy

Page 28

The random uncertainty in the results was calculated using the formula

Uncertainty=

Values
, this gave random uncertainties of 7% for colorimetric analysis
n values

and 1.6% for volumetric analysis.


e.g. for volumetric analysis

Unc=

96.992.1
=1.6
3

Iain Sword 604312723 Elgin Academy

Page 29

Appendix 2: Preparation of sodium thiosulphate


solution
Equipment:

100cm3 glass beaker (pyrex glass)


Balance (accurate to 3d.p. or more)
250cm3 volumetric flask

Reagents:

Crystals of Sodium thiosulphate


Deionised water as required

Method:
A mass of sodium thiosulphate was weighed in a weighing boat on a tared balance
and recorded. This was then transferred to a beaker and the weighing boat washed
with deionised water to provide washings. The crystals were then partially diluted and
transferred to the 250cm3 volumetric flask then made up to the 250cm3 mark,
stoppered then inverted.
The mass of sodium thiosulphate used was: 13.656g
The formula mass stated on this container of sodium thiosulphate crystals was: 248g/mol
To calculate the concentration, I first fount the number of moles:

m 13.656
=
Fm
248
n=0.055 mol
1000 n 10000.055
C=
=
V
250
1
C=0.22 mol .l
n=

Appendix 3: Calculation of the required volume of


KI solution (retrospectively)
To predict the average number of moles of copper in each conical flask I used the
following calculation:
Mass of copper is 97% the mass of each coin (average mass 3.6g)
Mass copper: 3.49g
Number of moles of copper=3.49/63.5
=0.055moles
Number of moles of copper per conical flask=0.0055moles

Iain Sword 604312723 Elgin Academy

Page 30

N O3

2+
The ratio of Cu ions to potassium iodide in the equation
is 2:4 or 1:2, so the

2+

2 Cu

number of moles required of KI is 0.011moles


The minimum required volume of 1mol.l-1 KI can now be calculated:
V=1000n/C=1000*0.011/1
V=11cm3

Appendix 4: References
http://www.royalmint.com/discover/uk-coins/coin-design-and-specifications/one-pennycoin, visited 29/01/15
http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Coordination_Chemistry/Ligands,
visited 29/01/15
http://www.docbrown.info/page07/appendixtrans09.htm, visited 29/01/15
Garvie D, Reid J & Robertson A, (1976) Core Chemistry, Oxford University Press, London,
Page 158.
http://home.freeuk.net/concord2/Transition_elements/Transition_Elements_notes_files/ima
ge032.jpg, visited 30/1/15
http://dwb.unl.edu/dwb/Meetings/Oct-8-99/ComplexIonsTutor.html, visited 30/1/15
http://blog.asmartbear.com/color-wheels.html, visited 4/3/15
http://www.titrations.info/iodometric-titration-copper, visited 4/2/15
http://www.csudh.edu/oliver/che230/textbook/ch04.htm, visited 4/2/15
Gibb A & Hawley D, (2010) BrightRED Revision Advanced Higher CHEMISTRY, Bright Red
Publishing, Edinburgh, page 25
http://www.jaytecglass.co.uk/laboratory-glassware/general-volumetricglassware/volumetric-flask/class-b-volumetric-flasks/, visited 21/2/15

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