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ChE 412L
Physical Chemistry Laboratory 2
Submitted by:
October 5, 2015
1.
INTRODUCTION
An electrochemical cell consists of two electrodes in contact with an electrolyte; an
electrode and its electrolyte make up an electrode compartment. There are two types of
electrochemical cell: galvanic, and electrolytic. Galvanic cells are electrochemical cells that
produce electricity as a consequence of a spontaneous reaction occurring inside it, while
electrolytic cells are electrochemical cells that require an external current source to drive a
non-spontaneous reaction forward [Atkins and de Paula, 2014]. Electrochemical cells are
most often used to decompose chemical compounds, in a process called electrolysis.
Electrolysis involves forcing a current through a cell to produce a chemical change
that is otherwise non-spontaneous. When an electric current is passed through the electrolyte
solution, ions move towards the electrodes. Since these ions have different mobilities in an
electric field, these ions contribute to charge transport. The transference (or transport)
number, then, is the fraction of the total current carried by an ion [Wilson et. al., 1968]. At
+/
) and charge (
+/
+/
+/
transport, ion mobility ( u
) and ionic conductivity (
):
q
t +/- =
t +/I
q
u
F ( n A n C )
2
q = q+ +q . Using the mass changes
z R F( m C m A )
q1 =
2M
q = It .
q M( n A n C )
=
q
zR ( m C m A )
=
t
and t+ = 1
t .
Cathode
2 H(aq ) +2 e H2 ( g)
Anode
2 H2 O O2 (g) +4 H+(aq) +4 e-
In the coulometer,
Cathode
Cu 2+
( aq) +2 e Cu ( s )
Anode
Cu (s ) Cu (aq ) +2e
2+
G =q
where
RT
lnQ
nF
The equation states that the cell potential is directly related to the change
in free energy between the reactants and products in the cell [Zumdahl
and Zumdahl, 2012]. This relationship is important because it provides an
experimental means to obtain G for a reaction. It also confirms that a cell
will spontaneously run in the direction that gives a positive value for cell; a
positive cell potential corresponds to a negative G, which is the condition
for spontaneity.
2.
OBJECTIVES
2.1 ION
To describe the reactions that occur in the cathode and anode regions of
2.2 ECR
electrochemical reactions
3.
METHODOLOGY
3.1 Materials
The materials used in the experiment were aqueous HNO 3 (69 w/w%, = 1.42
g/mL), solid NaOH (97 w/w%), aqueous H 2SO4 (96.5 w/w%, = 1.84 g/mL), solid
crystals of CuSO45H2O (99.5 w/w%) dried potassium hydrogen phthalate (C 8H5KO4
or KHP), methyl red and phenolphthalein indicator and distilled water (H 2O).
4
iron clamp
250 mL beaker
iron stand
5 mL pipette
copper electrodes
pipettors
carbon electrodes
3000 mL beaker
base buret
thermometer
digital stopwatch
transference vessel
connecting cords
power supply
multimeter
analytical balance
3.3 Procedure
The glassware to be used were first washed and dried thoroughly. Two different
solutions were to be prepared: 250 mL of 0.1 M HNO 3 and 0.5 M CuSO4/H2SO4
solution. The nitric acid solution was prepared by measuring out 1.61 mL of stock
HNO3 using a 10 mL graduated cylinder, pouring the measured quantity into a 250
mL volumetric flask that was half-filled with distilled water, and then filling the
volumetric flask with distilled water up to the 250 mL mark; the flask was then
shaken by inverting the flask and shaking the bulb while keeping the neck steady.
The acidified copper sulfate solution was prepared by measuring out 6.90 mL of
stock H2SO4 using a 10 mL graduated cylinder and pouring the measured quantity
into a 250 mL volumetric flask that was half-filled with distilled water; to this, an
aqueous solution containing 31.3675 g CuSO 45H2O was added and the resulting
solution diluted with distilled water to the 250 mL mark.
The 0.1 M NaOH solution that was on hand was standardized against
approximately 0.5 g potassium hydrogen phthalate (KHP) using phenolphthalein as
an indicator and two trials were performed; similarly, two 5.00 mL aliquots of the
prepared HNO3 solution were titrated against the standardized NaOH solution using
methyl red as an indicator to determine its initial concentration.
The transference apparatus was then set up. First, the three arms of the double Utube were filled with equal volumes (with the electrodes in place) of the prepared
nitric acid; the level was marked on the glass using a permanent marker. The
electrodes were then removed and the liquid level also marked on the glass. The Utubes central arm was then clamped onto the iron support rod and the double U-tube
submerged into the large water-filled beaker, ensuring that the marked level was
5
submerged in the water bath. The positive jack of the power supply was then
connected to the electrode terminal at the U-tubes left arm (transference anode).
At the same time, the copper coulometer was assembled. The copper sheets were
labeled according to which electrode they were to become, weighed dry, then fixed
onto the electrode holder. The electrodes were then submerged in a beaker containing
the acidified copper sulfate solution. A wire was connected between the electrode
terminal at the U-tubes right arm (transference cathode) to the slot at the electrode
holder for the left electrode (coulometer anode). A wire was connected between the
slot at the electrode holder for the right electrode (coulometer cathode) to the
multimeter ammeter jack, and another wire between the multimeter ground to the
power supply ground thus completing the circuit.
The power supply was then turned on and the electrolysis left to proceed for 90
minutes. Current readings from the multimeter and the water bath temperature were
taken every ten minutes. At the end of the electrolysis, a 5 mL electrolyte aliquot was
taken from each transference vessel electrode compartment and titrated against the
standardized NaOH to determine its concentration. The power was then turned off
and the set up dismantled. The double U-tube was then washed and the marked
volume of the anodic and cathodic regions determined by filling them with water up
to the mark, then pouring the water into a graduated cylinder for measurement. The
copper sheets were washed and dried thoroughly before weighing them again.
4.
Ion mobility
Four pieces of information are needed to determine the transference numbers of the
acid solution in the cathodic and anodic compartments of the transference vessel and the
change in the masses of the electrodes in the copper coulometer. Table 1 below shows the
change of concentration of the HNO3 in the cathodic and anodic compartments of the
transference vessel.
Table 1. Concentration changes in the transference vessel compartments
Compartment
(V = 22.8 mL)
Cathode
Anode
Molarity (M)
Before electrolysis After electrolysis
0.0601
0.0811
0.0981
The concentration determined here is the concentration of the hydronium ion in the
compartment; more H+ is present in the anode because it is the site where H + is produced and
since the hydronium ions move from the cathode to the anode, and less H + is present in the
cathode since H+ is reduced there to hydrogen gas.
In the coulometer, the copper electrodes change their masses during the electrolysis.
Table 2 below shows these changes.
Table 2. Mass changes of the copper coulometer electrodes
Mass (g)
Before electrolysis
After electrolysis
4.0406
4.0999
6.8404
6.7589
Electrode
Cathode
Anode
The reactions will be discussed further in the succeeding section. For this parts purposes, the
required information is now complete and the transference numbers are calculated. Two
methods of calculating the transference numbers will be compared: that when the value for q
is obtained using the mass changes of the copper electrodes, and that when the value for q is
given by q = It. For the second method the current values are plotted against time and fitted to
a curve, so that the total charge is actually given by
5400
q 2 = I dt =
0
5400
Table 3 shows the values of the transference values using both calculation methods; literature
values taken from the PHYWE discussion on the transference number apparatus.
Table 3. Transference numbers of the ions using two different calculation methods
Values using q1
Literature
values at 25C
Values using q2
experimental at
27C
Percent
error (%)
experimental at
27C
Percent
error (%)
t+
0.8300
0.8037
3.17
0.7531
9.27
0.1700
0.1963
15.47
0.2469
45.24
The transference numbers can be interpreted in terms of the mobilities of the ions involved.
Ion mobility is directly proportional to the speed at which the ion moves through the medium,
and this in turn is inversely proportional to the radius of the ion. Thus, an ion with a small
radius (such as the H+ ion) moves quickly through the solution, has a high mobility, and
7
carries more of the total charge; conversely, an ion with a large radius (such as the
N O3 )
moves slower through the solution, has lower mobility, and carries less of the total charge.
Additionally, a lighter ion can move faster than a heavier ion. The small difference between
the experimental and literature values (for the first method) is due to the different
temperatures at which the experiments were conducted. The second method gives values that
are farther away from the literature values, and this is because of the way that the total charge
is calculated; the first method uses the change of the masses of the copper coulometer
electrodes (which takes into account all of the fluctuations of the power supply) while the
second method depends on the current readings at each ten-minute interval (which does not
take into account any fluctuations within the intervals).
4.2
transference vessel and the reaction at the coulometer. It is to be noted that in an electrolytic
cell, the anode and cathode is still the site of oxidation and reduction, respectively, but the
anode carries the positive charge and the cathode the negative charge.
The reactions in the transference vessel are as follows:
Cathode
4 H+(aq ) +4 e- 2H 2 (g )
= 0
Anode
2 H2 O O2 (g) +4 H+(aq) +4 e-
= -1.23 V
The reactions explain why bubbles of gas were observed at both compartments: hydrogen
ions were being reduced to hydrogen gas at the cathode and water was being split into oxygen
gas and hydrogen ions at the anode. The stoichiometry of the reactions also explains why
more bubbles were observed at the cathode than at the anode: for every mole of oxygen gas,
two moles of hydrogen gas were produced. The cell potential is then
= = C + A = -1.23 V
and the change in the Gibbs free energy is given by
G =q
where q has already been calculated previously. The table below shows the values for the
change in free energy using the two values of the total charge calculated previously.
8
A difference of is observed between the values for G using different values of the total
charge. The positive value confirms that the reaction is indeed non-spontaneous.
At the coulometer, the reactions are:
5.
Cathode
Cu 2+
( aq) +2 e Cu ( s )
Anode
Cu (s ) Cu 2+
( aq ) +2e
CONCLUSION
The transference number is a quantity that can be used to determine other important
quantities, such as the charge transport and ion mobility. Hittorfs method is one way of
determining the transference numbers, and it involves using the concentration changes in the
anode and cathode because of the movement of ions. The calculated value of the hydronium
ion transference number is t+ = 0.8037 and the nitrate transference number is t_ = 0.1963.
There are many factors that affect the transference number, mass being one of them; a lighter
ion can move faster than a heavier ion through the medium, will transport more of the total
charge, and thus will have a greater transference number.
Oxidation-reduction reactions that occur in electrolytic cells are non-spontaneous and
need an external current source in order to be driven forward. In the transference vessel,
water is split into hydrogen and oxygen gas at the cathode and anode, respectively; in the
coulometer, copper metal is dissolved as copper (II) ions and redeposited as metal at the
anode and cathode, respectively. Because the reactions are non-spontaneous, a positive
change in free energy is observed.
6.
6.1
During the electrolysis of nitric acid, oxygen gas is produced at the anode and
hydrogen gas is produced at the cathode.
b) Write down the species involved in the electrolysis of nitric acid by determining the
reactions that occur in the cathode and anode regions of the U-tube.
+
Cathode
4 H(aq ) +4 e 2H 2 (g )
Anode
2 H2 O O2 (g) +4 H+(aq) +4 e-
Overall
reaction
2 H2 O O2 (g) + 2H 2 (g )
Values using q1
Literature
values at 25C
tH
N O
3
t
Values using q2
experimental at
27C
Percent
error (%)
experimental at
27C
Percent
error (%)
0.8300
0.8037
3.17
0.7531
9.27
0.1700
0.1963
15.47
0.2469
45.24
Heavier ions move slower than lighter ions through the medium and so transport
less of the total charge. Transport number is then inversely proportional to the
mass of the ion.
6.2
Cathode
4 H+(aq ) +4 e- 2H 2 (g )
10
Anode
2 H2 O O2 (g) +4 H(aq) +4 e
Overall
reaction
2 H2 O O2 (g) + 2H 2 (g )
The reaction stoichiometry shows that for every mole of oxygen gas, two moles of
hydrogen gas are produced at the electrodes. In the coulometer, the reactions are as
follows.
Cathode
Cu 2+
( aq) +2 e Cu ( s )
Anode
Cu (s ) Cu (aq ) +2e
2+
No overall reaction occurs at the coulometer, since the copper (II) ions produced at
the anode are then reduced to copper metal at the cathode.
b) What is the importance of the transference vessel and the coulometer in the
electrolytic determination of transference numbers?
c) Predict the mass changes in the copper electrodes if the nitric acid concentration in
the transference vessel is greater than 0.1 molar. Explain your answer.
The mass changes will be larger. Increasing the nitric acid concentration
increases the number of charge carriers available; with more charge carriers,
more charge can flow through the apparatus in the same span of time. The
increased charge will manifest itself as a greater mass change of the copper
electrodes.
d) Compare the calculated value of the total charge quantity from equation 6 with the
value obtained from q = It and discuss your answer.
The calculated value of the total charge using the copper electrode mass changes
is 213.80 C, while that of
attributed to the fluctuating current supply. The first method, involving the mass
changes of the copper electrodes, is much more accurate since the electrode mass
changes are proportional to the applied current; thus, the mass changes are
representative of the actual amount of current that has been used. The second
method, on the other hand, does not take into account the fluctuations in the
power supply as well as the first method does because the interval between each
current reading was 10 minutes and the current fluctuated significantly within
each interval.
e) Determine the change in the Gibbs free energy of the electrolysis of nitric acid.
= = C + A = -1.23 V
G =q = (213.80 C ) 1.23
7.
J
=262.98 J
C
REFERENCES
8.
APPENDIX
8.1 Variation of current with time
12
0.04
0.04
0.03
0.03
0.03
Current (A)
0.03
0.03
0.03
0.03
0.03
600
1200
1800
2400
3000
3600
4200
4800
5400
Time (s)
Mass KHP, g
Final buret reading, mL
Initial buret reading, mL
Volume NaOH dispensed, mL
NaOH concentration, M
Average NaOH concentration
TRIAL 2
0.5124
47.30
22.20
25.10
0.1000
0.1001 M
Volume HNO3, mL
Final buret reading, mL
Initial buret reading, mL
Volume NaOH dispensed, mL
HNO3 concentration, M
Average HNO3 concentration
FINAL
Cathode
Anode
5.0
5.0
41.7
38.7
38.7
33.8
3.0
4.9
0.0601
0.0981
n Ci = n Ai = VHN O M HN O =
3
mol
L )(0.0811
=1.85 10
(22.8
1000
L )
-3
mol
13
n Cf = VCHN O M CHN O =
mol
L 0.0601
=1.3710
(22.8
1000 )(
L )
A
n Af = V AHN O MHN
O =
mol
L)(0.0981
=2.2410
(22.8
1000
L )
mol
mol
m = 0.0593 g, m = 0.0815 g
For the first method,
= 0.8037
q
= 0.1963, t + =1t
q
=
t
For the second method,
5400
5400
q 2 = I dt =
0
= 0.7531
q
= 0.2469, t + =1t
q
=
t
8.5 Initial report attached.
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