ANALYSIS OF COPPER CONTENT IN COPPER ORES AND ACTIVE COMPOUND

IN SUNSCREEN LOTION TROUGH ULTRAVIOLET-VISIBLE

SPECTROPHOTOMETER
Ni Kadek Wahyuni Antari (1213031002)
Chemistry Education Department, Faculty of Mathematics and Natural Sciences
Universitas Pendidikan Ganesha
INTRODUCTION
Ultraviolet-visible spectroscopy is a method of analysis based on based on
molecular absorption by using ultraviolet radiation and visible light. The ultraviolet
radiation has wavelength between 160-400 nm and the visible light have
wavelength between 400-800 nm. Ultraviolet-visible spectroscopy is one type of
spectroscopy that provides a simple way to set a small quantity of a substance in
solution form. The principle of this spectroscopy is based on the interaction of
electromagnetic radiation energy to chemical substances [2]. This method is widely
used in quantitative measurement of organic and inorganic compounds. If certain
wavelengths of light absorbed by an atom or molecule, it will produce the spectrum
of absorption. Electronic structures of molecule determine the absorption light of
molecule.
Spectroscopy of molecule absorbance is based on the measurement of
transmittance T or absorbance A of a solution with concentration C in the
transparence cell with length of b cm. Absorbance position is related with radiation

wavelength ( ), whereas the energy is the same with energy needed for electronic
transition, while transmittance or absorbance is depend on the two factors, ability of
interaction between radiation energy and electronic system as well as difference
between ground state and excited state. Quantitatively, it can be stated as the
following Lambert-Beer equation:

I
I0
A = b c = - log T = - log

- log

= log

I0
I

I
bC
I0

whereas, A is absorbance , T is transmittance, I is light intensity emmited by

solution in cell, I0 is light intensity emmited by solvent in cell on same I.

is
-1
-1
comparator constant (L cm mol ), b is length of solution passed by light (generally,
1 cm) and C is concentration of absorbent species in mol L-1 (M) unit.
The examples of analysis by using UV-visible spectroscopy are analysis of the
copper in ore copper and active compound in sunscreen lotion. Copper (II) sulphate
pentahydrate (CuSO4.5H2O) is one of complex compound that has blue color. The
blue color of CuSO4.5H2O is caused by the metal involved and the number of d

orbital, associated with the oxidation state. The ions formed from Cu + ions are
generally colorless; while the ions formed from ion Cu 2+ is generally blue. This
happens because the configuration of Cu + ions that has electron configuration [Ar]
4s03d10, it appears that its 3d sub shell fully charged. While the configuration of Cu 2+
ions that has electron configuration [Ar] 4s 03d9, 3d sub shell was not fully charged.
This makes it possible to absorb light energy, which caused the excitation so that, it
can emit light energy that matches the color of light can be reflected when it
returns to the ground state. The structure of complex compound of CuSO 4.5H2O can
be seen as the following figure:
H2O

H2O
Cu 2+

H2O

H2O

2+

-O

O
S

H
H

-O
O
Picture 1. The Structure of complex compound of CuSO4.5H2O

In the case of copper (II) sulphate, 4 water molecules are covalently bonded
to form effectively a tetrahedral complex ion, [Cu(H2O)4]2+ and the 5th water
molecule H2O is hydrogen bonded to this ion and hydrogen bonded to a
neighbouring sulphate ion SO42- thus helping to hold the crystal lattice together,
though the main force of attraction is the electrostatic attraction between copper
complex ion and the sulphate ion.
Based on valence bond theory, the metal atom or ion under the influence of
ligands can use its (n1)d, ns, np or ns, np, nd orbitals for hybridisation, to yield a
set of equivalent orbitals of definite geometry such as octahedral, tetrahedral,
square planar, and so on. These hybridised orbitals are allowed to overlap with
ligand orbitals that can donate electron pairs for bonding. [8]
Table 1. Table of Valence Bond Theory
Coordinati
on number

Type of
hybridizati
on

Distribution of hybrid
orbitals in space

4
4
5
6
6

sp3
dsp2
sp3d
sp3d2
d2sp3

Tetrahedral
Square planar
Trigonal bipyramidal
Octahedral
Octahedral

Since [Cu(H2O)4]2+ is tetrahedral complex ion, so the hybridization become sp3. The
hybridization of complex ion of [Cu(H2O)4]2+ can be seen on the scheme below.

Orbital of Cu2+ ion

4s0

3d9

4p0

dsp2 hybridized orbital of Cu2+

3d9

Sp3 hybrid

3d9

For pair electrons of 4 H2O groups

[Cu(H2O)4]2+ complex

Picture 2.
The
Then, the energy level and the splitting orbital as follow:
Dxy Dxz

E
N
E
R
G
Y

Dyz

Dz2 Dx2-y2

Picture 3. The energy level and splitting d orbital of tetrahedral

Many modern technologies depend on the metal. Since it has become must
for a chemist to analyze ore to determine the content and developing methods for
the discovery of metal that has a commercial value. One of the important metals in
technology and economic value is copper, widely used for conductors, water pipes,
and a mixture of other metals known as alliances (such as brass, bronze and silver).
Spectrophotometry is widely used in analytical laboratories. Most laboratories
require identification and determination of organic compounds and inorganic (e.g.
pharmaceuticals, fertilizers, mining etc.) by using a spectrophotometer [3]. In this
experiment will be determined percentage of mass of copper in copper ore by using
spectroscopic techniques. If w is the mass of copper ore was taken and 100 mL is
the total volume of solution, so the percentage of copper in ore copper is as follows.

0.10 x C x 63.55 x 100

= mass
w
Besides, active compound in sunscreen lotion is also can be analysis by using
UV-visible spectroscopy. The sun emits electromagnetic radiation to the earth with a
range of 290 nm to 800 nm. The ultraviolet radiation has wavelength between 160400 nm. So, the ultraviolet radiation is also emitted by the sun. There are two types
of ultraviolet radiation, UV A and UV B. The range of UV A is approximately 320-400
nm and UV-B approximately 280-320 nm. Ultraviolet is very dangerous for skin.
Therefore, skin must be protected with sunscreen lotion to avoid radiated directly on
the skin of the tropical sun. UV-B is responsible for skin damage (sunburn and
tanning). When skin is exposed to ultraviolet radiation, skin cells will produce a
brown pigment called melanin and will become more brown skin and thinning. More
and more subject to ultraviolet radiation in the range 290-320 nm the more melanin
is formed and the skin will be darker. Furthermore, ultraviolet radiation causes skin
damage to DNA and proteins, thus causing a very dangerous effect are skin cancer
or melanoma [3].
Sunscreen lotion is a product containing a compound that can absorb, scatter
or reflect sunlight on the skin, so it can be used to protect the function and structure
of human skin from damage caused by sunlight. Kaemferia galanga L. is one of the
many traditional medicinal plants contain natural ingredients compounds, one of
them is ethyl p-methoxycinnamate is the main content of Kaemferia galangal L.
Ethyl p-methoxycinnamate (EPMS) is one of the compounds that are the basic
ingredients of sunscreen lotion that protects skin from UV radiation. EPMS included
in the class of ester compounds containing benzene ring and the non-polar methoxy
group and the carbonyl group which binds less polar ethyl [4].
O
OC 2H5
H3CO

Picture 4. The structure of EPMS

Every molecule can absorb radiation in certain wavelength with different
absorbance including molecules that have conjugation system. The more bond it
has, the closer gap between highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO), thus the lower energy it absorb from the
radiation. EPMS, which has 5 electron pairs in its conjugation system, can absorb
UV-B radiation with high absorbance.
When bonds in its conjugation system absorb UV-B radiation, the excitation
process in where electron in bond moves from highest occupied molecular orbital
(HOMO) to LUMO, is begun. It absorbs energy at wavelength of 309.5 nm to do the
excitation process. [7]

Picture 5. Excitation process of eugenol

The objectives of this experiment were 1) to make standard curve and analysis
of copper content in a copper ore and 2) to analyze active compound contained in
sunscreen lotion (Citra Body Lotion).
METHODS
1. Materials and Equipment
This experiment was conducted by using several equipment and materials.
Equipment used in this experiment were beaker 100 mL (6 pieces), watch glass
(1 piece), spatula, stirrer rod, volumetric flask 100 mL (1 piece), volumetric flask
50 mL (1 piece), volumetric flask 25 mL (2 pieces), and volumetric flask 10 mL
(2 pieces), graduated pipette 10 mL (1 piece), and drop pipette (1 piece). Then,
materials used in this experiment were CuSO 4 hydrate (1.2475 grams), aquades
(as needed), copper ore (0.502 grams), concentrated H 2SO4 (as needed),
ethanol (as needed), and Citra Body Lotion (as needed). The instrument used
was UV-Vis spectrophotometer.
2. Procedure
2.1Analysis CuSO4.5H2O as Standard Solution
A total of 1.2475 grams of CuSO 4.5H2O were dissolved in 50 mL of aquades.
Then, its solution was diluted until the concentration 0.02 M, 0.04 M, 0.06 M,
and 0.08 M. Theirs solution were prepared as a standard. Then, the absorbance
of standard solution was measured by using UV-visible spectrophotometer.
2.2Analysis Copper Content in Copper Ore
A total of 0.502 grams of copper ore was weighed and placed in beaker
100 mL. Then, the copper ore was added by 2 mL of concentrated sulfuric acid
drop by drop. The reaction was waited until it was stopped and then continued
by adding more sulfuric acid until all copper were soluble. The mixture was
heated slowly until it boils for 1-2 minutes for complete reaction. Solution was
cooled and it was added by 10 ml of aquades. It was kept a few minutes until
produce precipitate as the contaminant, and then it was separated by

decantation. The filtrate entered into the volumetric flask 100 mL and it was
added by aquades until reach the scale. The solution was shaken in order to get
homogeneous solution. The absorbance of the solution was measured by using
UV-Vis spectrophotometer.
2.3Analysis of Active Compound in Citra Body Lotion
Small amount of Citra Body Lotion was diluted into ethanol in beaker. Then
the absorbance was measured by UV-Vis spectrophotometer.

RESULTS AND DISCUSSION

Analysis CuSO4.5H2O as Standard Solution
In this experiment, it was made sample solution of CuSO4 0.1 M as much as
50 mL by weighing a total of 1.2475 gram of solid CuSO4.5H2O. The color of
CuSO4.5H2O is bluish color because CuSO4.5H2O is a complex compound that has
bluish color. Ions are formed in the solution in the form of Cu2+ ions that are
generally blue. This occurs because of the configuration of Cu2+ ions (4s03d9), 3d
orbitals are not fully charged. This allows it to absorb light energy, which is caused
by the excitation of electrons that can emit light energy that matches the color of
light that can be reflected when you return to the ground state. Cu2+ ions have 3d9
configuration, which is causing Cu2+ cation has coordination number 6. In water,
CuSO4 solution is in the form of the complex [Cu(H2O)4]2+ can be written
CuSO4.5H2O.
H2O

H2O
Cu 2+

H2O

H2O

2+

-O

O
S

H
H

-O
O
Picture 2. The Structure of Complex Compound of CuSO4.5H2O

In the case of copper (II) sulphate, 4 water molecules are covalently bonded
to form effectively a square planar complex ion, [Cu(H2O)4]2+ and the 5th water
molecule H2O is hydrogen bonded to this ion and hydrogen bonded to a
neighbouring sulphate ion SO42- thus helping to hold the crystal lattice together,
though the main force of attraction is the electrostatic attraction between copper
complex ion and the sulphate ion. Therefore, the water of crystallization number
doesn't equal the co-ordination number of the central metal ion.
[Cu(H2O)4]2+, H2O, SO42- are the three components of the crystal structure of
copper (II) sulfate pentahydrate, and all three are linked by hydrogen bonds. The full
structure is a bit complicated to draw but the 5 th and 6th octahedral positions of the
Cu2+ ion are occupied by oxygen atoms of the sulfate ion and the 5 th water molecule
is held in position by hydrogen bonding. However, this blue crystal lattice is readily

broken down on heating, a classical demonstration of a reversible reaction, since

the white anhydrous solid turns blue on adding water.

Cu SO 4. 5 H 2 O Cu SO 4 + H 2 O

Furthermore, theories of crystal field can explain the color that is produced in
complex compound, involving d orbital in transition metal ion (copper ion). Based on
this theory, orbital d that has same energy will be broken by the influence of ligand
field. So, it makes there is four energy level for d orbital in square planar ligand
field. Square planar coordination is rare except for d 9 metals ion like copper (II) ion.

Picture 3. Splitting d Orbital of Square Planar

Electrons are located in the dx2-y2 orbital undergo repulsion of the four ligands are
located on the x-axis and y; while the electron in dz2 orbital only suffered repulsion
of two ligands which place on the z axis. If the ligand field is strong enough, then
the energy difference between these two orbitals (orbitals dx2-y2 and dz2) becomes
greater than the energy required for electron pairing.
In such conditions, the complex will be more stable if the dx2-y2 orbitals empty
and both electron should occupy eg orbitals arranged in pairs on dz2 orbitals. Thus,
four ligands can be bound in a complex on the x-axis and y to be easier because it
does not undergo repulsion of dx2-y2 empty orbital. Instead, ligand cannot approach
the metal center through the z-axis, due to a very strong repulsion of charged two
dz2 orbital electrons. Therefore only four bonds formed between the metal center
with the ligand, and the geometric structure to a square planar complex. This
splitting energy is same with energy in visible light, so the copper ion in copper (II)
sulphate produce the blue color on that complex compound [1].

Before doing measurement of absorbance by using UV-Vis spectrophotometer,

the sample solution was diluted in order to obtain the concentration of 0.02 M; 0.04
M; 0.06 M; 0.08 M respectively. The calculation can be seen as follows:
-Making of CuSO4 solution from CuSO4.5H2O powder

M=

mass 1000

Mr
V

0.1=

0.1=

mass 1000

249,5 100

0.1=

mass 1000

249,5
50

mass 1000

249,5
50

Mass = 1.2475 gram

So, it was needed 1.2475 gram of solid CuSO4.5H2O to make 50 mL of CuSO4 0.1 M
solution.
-Making of CuSO4 solution 0.02 M
V 1 x M 1 = V2 x M 2
V1 x 0.1 M = 25 mL x 0.02 M
V1 = 5 mL
So, in order to make 25 mL of CuSO4 solution 0.02 M , it was diluted CuSO4 0.1 M as
much as 5 mL.
-Making of CuSO4 solution 0.04 M
V 1 x M 1 = V2 x M 2
V1 x 0.1 M = 25 mL x 0.04 M
V1 = 10 mL
So, in order to make 25 mL of CuSO4 solution 0.04 M , it was diluted CuSO4 0.1 M as
much as 10 mL.
-Making of CuSO4 solution 0.06 M
V 1 x M 1 = V2 x M 2
V1 x 0.1 M = 10 mL x 0.06 M
V1 = 6 mL
So, in order to make 10 mL of CuSO4 solution 0.06 M , it was diluted CuSO4 0.1 M as
much as 6 mL.
-Making of CuSO4 solution 0.08 M
V 1 x M 1 = V2 x M 2
V1 x 0.1 M = 10 mL x 0.08 M
V1 = 8 mL
So, in order to make 10 mL of CuSO4 solution 0.08 M , it was diluted CuSO4 0.1 M as
much as 8 mL.
The following table shows the data of standard solution absorbance using UV-Vis,
but before that, it is explaining how to calculate the light intensity emitted by
solution. Since I0 is the light intensity emitted by solvent and the value is
represented by 100. Then absorbance is equal to - log I/Io, so
A
= - log I/Io
0.242 = - log I/100
-0.242

A
= - log I/Io
0.493 = - log I/100
= log I/100 -0.493= log I/100

I/100 = 10M -0.242

I/100 = 0.572
I
= 57.2

I/100
I/100
I

A
=
0.750 =
-0.750
I/100 =
I/100 =
I
=

A
= -log I/ Io
0.993 = - log I/100
= log I/100 -0.993= log I/100
I/100 = 10M -0.993
I/100 = 0.102
I
= 10.2

- log I/Io
- log I/100
10M -0.750
0.178
17.8

= 10M -0.493
= 0.321
= 32.1

Here is the table of the relation of Cu standard solution with absorbance.

Tabel 01. Measurement of standard solution
Concentration (M)
A
B
C
0.02
0.04
0.06
I
57.2
32.1
17.8
Io
100
100
100
I/Io
0.572
0.321
0.178
-log(I/Io)
0.242
0.493
0.750

D
0.08
10.2
100
0.102
0.993

Based on data above, it can be made calibration curve of standard solution

between concentration and absorbance as follows:

The Relation Curve between Concentration and Absorbance of Copper

absorbance

absorban
ce
Linear
(absorban
ce)

concentration

Graph 1. Calibration curve of Cu standard solution

The curve of concentration toward absorbance of standard solution is
appropriate to Lambert-Beer law. The absorbance increase as the increasing of
concentration, in which the line equation y = 12.55x 0.008 and R = 0.9999.
Therefore, the gradient is 12.55. Based on this equation, the (coefficient) of
standard solution can be calculated as follow.
Standard solution A (A= 0,242)

A = .b.C
0,242 = x 1 cm x 0,02 mol/L

0,242
0,02 mol L1cm

= 12.100 L mol-1 cm-1

Standard solution B (A= 0.493)
A = .b.C
0,493 = x 1 cm x 0,04 mol/L

0,493
0,04 mol L1cm

= 12.325 L mol- 1 cm-1

Standard solution C (A= 0.750)
A = .b.C
0,750 = x 1 cm x 0,06 mol/L

0,750
0,06 mol L1cm

= 12.500 L mol- 1 cm-1

Standard solution D (A= 0.993)
A = .b.C
0,993 = x 1 cm x 0,08 mol/L

0,993
0,08 mol L1cm

= 12.412 L mol- 1 cm-1

From the calculation above, it can be seen that the unit of extingsi, , is L cm-1 mol-1.
Analysis Copper Content in Copper Ore
From standard data above, it is obtained the calibration curve and also the line
equation that can stated as follows.
y = 12.55x 0.008
where y represented as absorbance, x represented concentration. Therefore, by
knowing the absorbance, it can be calculated the concentration. The mass of copper
ores used was 0.502 grams. The absorbance of the copper ore is obtained 0.567.
Therefore the concentration can be calculated as follows:
y
= 12.55x 0.008
0.567 = 12.55x 0.008
12.55x = 0.567 + 0.008
x
= 0.0458

So, the concentration of CuSO 4 solution is 0.0458 M. Then, it can be calculated

the mass percentage can be calculated as follows:

mass of Cu=

0.10 C Ar Cu
100
w

mass of Cu=

0.10 0.0458 63.55

100
0.502

mass of Cu=57.979
So the mass percentage of copper ores is 57.979%.
Analysis of Active Compound in Citra Body Lotion
Sunscreen lotion is designed to protect skin from damage caused by UV rays
from the sun. Some products of sunscreen lotion are determined the SPF (Sun
Protection Factor) value which can be considered as a factor of time to protect the
skin compared to exposure without any protection. The higher SPF values are
considered better. But only provide protection against UV-B (ultraviolet B), it does
not protect the skin against UV-A (ultraviolet A).
Sunscreen lotions contain active compounds that can absorb UV-B rays namely
oktilmetoksisinamat, butilmetoksisinamat and ethyl parametoksisinamat. In this
experiment, the wavelength of maximum absorption of sunscreen lotion on the
compound is measured. Sunscreen lotion that used in this experiment is Citra Body
Lotion which is dissolved in ethanol. In this case ethanol is used because its an
organic solvent, other reason that ethanol has no absorption in the wavelength
region of 200-1000 nm. The maximum wavelength and absorbance curve of Citra
Body Lotion and Ethyl-p-Methoxycinnamate can be seen as follows.

Picture 4.The absorbance of Citra Body

Lotion

Picture 5. The absorbance of Ethyl-pMethoxycinnamate

Table 2. The spectrum and effectiveness to absorb UVB of Citra Body Lotion and
EPMS
Citra Body Lotion
Ethyl-pMethoxycinnamate
Maximum absorbance, 0,168, 357 nm
0,544, 310 nm
max

Effectivity to absorb UVB

Not effective

Effective

Ethyl p-Methoxycinnamate is compound that can be isolated from Kaemferia

galanga L. From the curve and the table above, it is known that the maximum
absorbance of Ethyl-p-Methoxycinnamate is existed in 310 nm. This absorbance is
existed in UV-B absorbance area (280-320 nm), therefore the compounds can
absorb UV-B radiation. UV-B radiation is responsible for skin damage and skin
cancer. So, the Ethyl-p-Methoxycinnamate can be used as sunscreen lotion. In the
solution of EPMS is colorless, it because of the maximal wavelength of EPMS is 310
nm and it is not in the range of visible light that have wavelength between 400-800
nm.
In this experiment, Citra Body Lotion that existed in the market was tested by
diluting a small amount of body lotion to the ethanol. Then, it is tested by UV-Vis
spectrometer and it is known from the curve that the maximum absorbances are
existed in 357 nm. This maximum absorbance is not in the range of UV-B radiation
(280-320 nm), but its absorbance is included in the range of UV-A radiation (320400 nm). So, Citra Body Lotion contains active compound that can absorb UV-A
radiation.
CONCLUSIONS
Based on the result and discussion above, so it can be conclude that:
1. The standard curve can be obtained as follow:
The Relation Curve between Concentration and Absorbance of Copper
1.2
1

f(x) = 12.55x - 0.01

R = 1

0.8

absorbance

0.6

absorbance
Linear
(absorbance)

0.4
0.2
0
0

0.05

0.1

concentration
The line equation from the curve above can be stated: y = 12.55x 0.008.
From the line equation, the concentration of CuSO4 solution can be calculated

that is 0.0458 M. Furthermore, it can be known the mass percentage of

copper ores is 57.979%.
2. The maximum absorbances of Citra Body Lotion are existed in 357 nm. This
maximum absorbance is not in the range of UV-B radiation (280-320 nm), but
its absorbance is included in the range of UV-A radiation (320-400 nm). So,
Citra Body Lotion contains active compound that can absorb UV-A radiation.
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2. Muderawan, I. W. 2009. Analisis Instrumen. Undiksha Press: Singaraja.
3. Muderawan, I. W. Jurnal Praktikum
4. Tanjung, Mulyadi. 1999. Senyawa Tabir Surya yang Efektif dengan Bahan Baku
Senyaea Aktif dari Rimpang Kencur (Kaempferia galang L). Fakultas MIPA:
Universitas Airlangga.