Experiment 3: Determination of Avogadro’s Number using Electrogravimetry

Objective:

The objective of this experiment is to make an experimental measurement of Avogadro's number

using an electrochemical technique (electrogravimetry).

20 V - Power supply, U-tube, copper electrodes, electrical wires with crocodile

Apparatus:
clips, retort stand with clamps, emery paper, 4-decimal analytical balance.
Chemicals: 1M CuSO4 and 0.5M H2SO4

PRINCIPLES

The atomic mass of an element in grams is equal to one mole of the element. Chemists used
this definition of a mole long before they were able to measure the masses of individual atoms or
had the means to count atoms. The determination of Avogadro's number, which is the number of
particles in a mole, required the development of accurate and suitable measuring devices that
were not in existence until the early part of the twentieth century. The mole is considered a
fundamental unit has been adopted into the SI system as a basic unit of quantity. In this
experiment we will make a careful measurement of electron flow, amperage, and time to obtain
the number of electrons passing through the electrochemical cell. The electron flow, in amperes,
is usually referred to as the current. The number of atoms in a weighed sample can be related to
the number of electrons used and from that the value called Avogadro's number can be
calculated.

Avogadro's number can be determined in a number of different ways. This experiment will use
an electrochemical process called electrolysis via electrogravimetric technique. The
experimental setup for this process is called an electrolytic cell.

An electrolytic cell is made up of the following:

1. a source of direct current such as a battery or power supply.

2. insulated wires to carry the electric current.
3. two electrodes. (In this experiment both electrodes are copper metal. The electrode
connected to the negative (-) pin of the power supply is the cathode and the electrode
connected to the positive (+) pin of the power supply is the anode.)
4. a solution of sulfuric acid. (Sulfuric acid in this experiment is the conducting medium in
the cell and is called the electrolyte.)

The electrolytic process is used to determine the number of electrons needed to convert one mole
of copper atoms to one mole of copper ions, Cu2+. This number divided by two represents the
number of atoms converted from copper metal to copper ions:

Cu → Cu2+ + 2e
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This process, which involves the loss of electrons, is called oxidation. The number of copper
atoms per mole of copper is Avogadro's number, the value to be determined. The number of
electrons consumed in the process is determined by using the charge of an electron and the total
charge measured. The charge of an electron was determined in the famous Millikan oil-drop
experiment to be 1.60217733 x 10-19 coulombs per electron.

The number of coulombs used in the experiment can be calculated from the relationship: one
ampere = 1 coulomb/second. An ammeter is used in the experiment to measure the amperage and
a clock or stopwatch is used to measure the time in seconds. The mass of copper that reacts can
be determined by measuring the mass of the anode and the cathode before and after the
electrolysis.

In the electrolytic cell contains both copper electrodes and the electrolyte is 1M CuSO 4 + 0.5 M
H2SO4. In the course of the electrolysis, the copper electrode (the anode) connected to the
positive pin of the power supply loses mass as the copper atoms are converted to copper ions.
This loss of mass is visible to the eye after a while as pitting of the surface of the metal electrode.
Also the copper ions, Cu2+ , produced, immediately pass into the water solution and deposit on
the cathode as the following reaction:

Cu2+ + 2 electrons → Cu (solid).

It is also possible to measure the copper deposited and use it to calculate Avogadro's number.

EXAMPLE

Anode mass lost: 0.3554 grams (g)

Current(average): 0.601 amperes (amp)

Time of electrolysis: 1802 seconds (s)

Note: one ampere = 1 coulomb/second or one amp.s = 1 coul

charge of an electron 1.602 x 10-19coulomb

Step 1.

Find the total charge passed through the circuit.

(0.601 amp)(1coul/1amp-s)(1802 s) = 1083 coul

Step 2.

Calculate the number of electrons in the electrolysis.

(1083 coul)( 1 electron/1.6022 x 10 -19coul) = 6.759 x 10 21electrons

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Step 3.

Determine the number of copper atoms lost from the anode. Recall the electrolysis process
consumes two electrons per copper ion formed. Therefore the number of copper(II) ions formed
is half the number of electrons.

Number of Cu+2 ions = number of electrons measured , namely,

(6.752 x 10 21 electrons)(1 Cu+2 / 2 electrons) = 3.380 x 10 21 Cu+2 ions

Step 4.

Calculate the number of copper ions per gram of copper from the number of copper ions above
and the mass of copper ions produced. The mass of the copper ions produced is equal to the mass
loss of the anode. ( The mass of the electrons is so small that it is negligible in this measurement,
therefore the mass of the copper (II) ions is the same as copper atoms.)

Thus: mass loss of electrode = mass of Cu+2 ions = 0.3554 g

3.380 x 10 21 Cu+2 ions / 0.3544g = 9.510 x 10 21 Cu+2 ions/g

= 9.510 x 10 21 Cu atoms/g

Step 5.

Calculate the number of copper atoms in a mole of copper, 63.546 grams.

21
Cu atoms /mole of Cu = (9.510 x 10 copper atoms/g copper)(63.546 g/mole copper)

= 6.040 x 10 23 copper atoms/mole

This is the student's measured value of Avogaro's number.

Step 6.

Calculate the percent error.

Absolute error: |6.02 x 10 23 - 6.04 x 10 23 | = 2 x 10 21

Percent error: (2 x 10 21 / 6.02 x 10 23)(100) = 0.3%

PROCEDURE
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Obtain two copper electrodes. It is may be necessary to first polish and clean the electrodes
before any measurements are taken.

Do not touch the electrodes with your fingers. Dip the electrodes in a beaker of clean tap water
then dip the electrode in the beaker labeled alcohol. Let the electrodes dry on a paper towel.
When the electrodes are dry, put a sticker on each electrode before weighing. Weigh them
carefully on the analytical balance to the nearest 0.0001 gram. Label the electrode with less
weight as anode.

The electrolytic solution is 1M CuSO4 in the 250-mL beaker.

Before making any connections be sure the power supply is off and unplugged. The power
supply must be set at 20 V. The correct sequence requires the positive pole of the power supply
be connected to the anode of the first cell. The cathode is next connected to the positive pin of
the ammeter. Have your apparatus approved by the instructor before you turn on the power!

When the apparatus is approved, plug in the power supply. Make sure the power supply is in the
off position. Accurate measurements of the time in seconds and the current in amperes are
essential for good results. The amperage should be recorded at 30sec intervals for 10 min. The
amperage may vary over the course of the experiment due to changes in the electrolyte solution,
temperature, or position of the electrodes. The amperage used in the calculation should be an
average of the readings taken. The current should flow a minimum of 10 mins. After 10 mins
turn off the power supply record the last amperage value and the time.

Now that the electrolysis has stopped you will need to retrieve the anode and cathode from the
cell, rinse gently with distilled water. Dry them as before by immersing them in alcohol and
allowing them to dry on a tissue paper or towel. DO NOT WIPE THE ANODE AND
CATHODE WITH A TISSUE OR TOWEL. If you wipe them you will remove copper from the
surface and invalidate your work.

Repeat the experiment for second readings. Use the same electrodes, re-polish the electrodes
with emery paper and re-weigh.

Repeat the electrolysis process using 0.5M H2SO4 solution. Record your observations on what
occuring at the electrodes and electrolyte solution. Caution-this solution is corrosive and will
damage skin and clothing on contact.

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 ELECTROLYSIS DATA

ELECTRODE MEASUREMENTS

Trial 1 Trial 2
Mass of anode before electrolysis 47.7479 47.6897
Mass of anode after electrolysis 47.7012 47.6512
Mass loss of anode (g) 0.0467 0.0385

Trial 1 Trial 2
Mass of cathode before electrolysis 48.3982 48.4196
Mass of cathode after electrolysis 48.4512 48.4738
Mass gain at cathode (g) 0.053 0.0542

Average of weight loss at anode: 0.0426 g

Average of weight gain at cathode: 0.0536 g

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 TIME-AMPERAGE MEASUREMENTS

Trial 1 Trial 2
Time (Secs) Current (A) Current (A)
0 0.189 0.252
30 0.186 0.240
60 0.184 0.235
90 0.184 0.235
120 0.184 0.235
150 0.185 0.236
180 0.186 0.238
210 0.187 0.240
240 0.188 0.241
270 0.189 0.243
300 0.191 0.245
330 0.192 0.248
360 0.193 0.249
390 0.195 0.250
420 0.196 0.252
450 0.197 0.254
480 0.198 0.256
510 0.200 0.257
540 0.201 0.259
570 0.203 0.261
600 0.204 0.263
Average Current 0.192 0.236

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 SUMMARY OF DATA AND RESULTS

Table 1:

Trial 1 Trial 2
Total time of electrolysis (seconds) 600 600
Average current during electrolysis (amperes) 0.192 0.236
Total charge measured (coulombs), Q 115.2 141.6
Number of electrons passed 7.190 x 1020 8.838 x 1020
Number of Cu2+ ions generated 3.595 x 1020 4.419 x 1020

Based of weight loss of anode (Table 2):

Trial 1 Trial 2
Number of Cu2+ ions/gram Cu metal (Cu2+/g 7.698 x 1021 1.1478 x 1022
Cu)
Avogadro's number (from your measurements) 4.892 x 1023 7.295 x 1023
Avogadro's number ( true or accepted value) 6.022 x 1023 6.022 x 1023
Absolute error in measured value 1.13 x 1023 1.273 x 1023
Relative % error in measured value 18.76% 21.14%

Based of weight gain of cathode (Table 3):

Trial 1 Trial 2
Number of Cu2+ ions/gram Cu metal (Cu2+/g 9.338 x 1021 6.633 x 1021
Cu)
Avogadro's number (from your measurements) 5.934 x 1023 4.215 x 1023
Avogadro's number ( true or accepted value) 6.022 x 1023 6.022 x 1023
Absolute error in measured value 8.8 x 1021 1.807 x 1023
Relative % error in measured value 1.45% 29.96%

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Calculation for Table 1:

Q = It

Trial 1

Q = (0.192amp-s)(1 coul/1amp-s)(600s)

= 115.2 coul

Trial 2

Q = (0.236amp-s)(1coul/1amp-s)(600s)

= 141.6 coul

No. of e = Q/e

Trial 1 Trial 2

No. of e = 115.2 / 1.6022 x 10-19 No. of e = 141.6 / 1.6022 x 10-19

= 7.190 x 1020 electrons = 8.838 x 1020 electrons

No. of Cu2+ ions = no. of e x no of e in one atom

Trial 1

No. of Cu2+ ions = 7.190 x 1020 x (1 Cu2+ / 2 electrons)

= 3.595 x 1020 ions

Trial 2

No. of Cu2+ ions = 8.838 x 1020 x (1 Cu2+ / 2 electrons)

= 4.419 x 1020 ions

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Calculation for Table 2

No of Cu2+ ions/gram = No. of Cu2+ ions / Mass loss of anode

Trial 1

No of Cu2+ ions/gram = 3.595 x 1020 ions / 0.0467

= 7.698 x 1021 Cu2+ ions/g

= 7.698 x 1021 Cu atoms/g

Trial 2

No of Cu2+ ions/gram = 4.419 x 1020 ions / 0.0385

= 1.1478 x 1022 Cu2+ ions/g

= 1.1478 x 1022 Cu atoms/g

Avogadro's number (from your measurements) = Cu atoms x mole of Cu

Trial 1

Avogadro's number = 7.698 x 1021 Cu atoms/g x 63.546 g/mole copper

= 4.892 x 1023 atoms/mole copper

Trial 2

Avogadro's number = 1.1478 x 1022 Cu atoms/g x 63.546 g/mole copper

= 7.295 x 1023 atoms/mole copper

Absolute error in measured value = true value NA – measured NA

Trial 1

Absolute error in measured value = |6.022 x 1023 - 4.892 x 1023|

= 1.13 x 1023

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Trial 2

Absolute error in measured value = |6.022 x 1023 – 7.295 x 1023|

= 1.273 x 1023

Relative % error in measured value = (Absolute error / true value of NA) x 100%

Trial 1

Relative % error in measured value = (1.13 x 1023 / 6.022 x 1023) x 100%

= 18.76%

Trial 2

Relative % error in measured value = (1.273 x 1023 / 6.022 x 1023) x 100%

= 21.14%

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Calculation for Table 3

No of Cu2+ ions/gram = No. of Cu2+ ions / Mass gain at cathode

Trial 1

No of Cu2+ ions/gram = 3.595 x 1020 ions / 0.0385

= 9.338 x 1021 Cu2+ ions/g

= 9.338 x 1021 Cu atoms/g

Trial 2

No of Cu2+ ions/gram = 3.595 x 1020 ions / 0.0542

= 6.633 x 1021 Cu2+ ions/g

= 6.633 x 1021 Cu atoms/g

Avogadro's number (from your measurements) = Cu atoms x mole of Cu

Trial 1

Avogadro's number = 9.338 x 1021 Cu atoms/g x 63.546 g/mole copper

= 5.934 x 1023 atoms/mole copper

Trial 2

Avogadro's number = 6.633 x 1021 Cu atoms/g x 63.546 g/mole copper

= 4.215 x 1023 atoms/mole copper

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Absolute error in measured value = true value NA – measured NA

Trial 1

Absolute error in measured value = |6.022 x 1023 – 5.934 x 1023|

= 8.8 x 1021

Trial 2

Absolute error in measured value = |6.022 x 1023 – 4.215 x 1023|

= 1.807 x 1023

Relative % error in measured value = (Absolute error / true value of NA) x 100%

Trial 1

Relative % error in measured value = (8.8 x 1021/ 6.022 x 1023) x 100%

= 1.45%

Trial 2

Relative % error in measured value = (1.807 x 1023/ 6.022 x 1023) x 100%

= 29.96%

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Questions:

1. Calculate the charge passed efficiency, Qa/Qc (%) during the electrolysis.

Trial 1:
At anode, 0.0467g = (63.54 g/mol x Q)/(2e x 96500 C/mol)
Qa = 141.85 C

At cathode, 0.053g = (63.54 g/mol x Q)/(2e x 96500 C/mol)

Qc = 160.99 C

Charge passed efficiency, Qa/Qc x 100% = 88.11%

Trial 2:
At anode, 0.0385g = (63.54 g/mol x Q)/(2e x 96500 C/mol)
Qa = 116.94 C

At cathode, 0.0542g = (63.54 g/mol x Q)/(2e x 96500 C/mol)

Qc = 164.63 C

Charge passed efficiency, Qa/Qc x 100% = 71.03%

2. Through your observations, differentiate between electrolysis of 0.5M H 2SO4 solution and
1M CuSO4 solution.

Through my observation, the net loss and gain for the Cu ions were found to be higher in H 2SO4
compared in CuSO4. It was also found that the cathode thickness in H2SO4 more than the
cathode in CuSO4.

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Discussion:

“Electrogravimetry is electroanalytical method based on gravimetric determination of metallic

element, which are isolated on the cathode in form of metal or on the anode in form of metal
oxide during electrolysis. This method employs two or three electrodes, and either a constant
current or a constant potential is applied to the preweighed working electrode.”(University of
Wroclaw, no date).

The determination of Avogadro’s number was done through electrogravimetric technique.

However, percentage error for each electrolyte was found to be highand nearing 100%. The
values were 1.45% and 29.96% for Trial 1 and Trial 2 respectively, in CuSO4.

Experimentally, the net loss and gain ions in CuSO 4 can be justified with the half reactions
below:

Anode : Cu(s) → Cu2+(aq) + 2e-

O2 + 4H+ + 4e- → 2H2O
Cathode : 2H2O + 2e- → H2(g) + 2OH-
Cu2+(aq) + 2e- → Cu(s)

at anode, due to the fact that the position of OH - in the standard reduction potential (SRP) list is
lower than the SO42-, therefore, OH- was much easier to be discharged compared to SO 42-.
Whereas at Cu2+ was discharged due to its higher ability to be discharged compared to H+.

Here, it is clearly shown that the Cu 2+ ions needed to copete only with H+ ions, however Cu2+
ions would definitely be discharged easily. Higher chances of Cu 2+ ions to be reduced caused the
deposition of Cu to be high, say, more efficient. On the ither hand, there was a slight difference
that occured.

When a very small external current is applied to the copper electrodes, then the equilibrium
between Cu2+ in the solutiion and the Cu of the elctrodes is disturbed. Copper goes into solution
at the anode and an equivalent amount of copper ions are deposited at the cathode (PHYWE, no
date). Theoretically, there is no change in the total amount of dissolved copper sulphate but
experiment showed otherwise. The net loss and gain for the electrode did not tally. The mass loss
by anode was lower compared to the mass gained by the cathode. The possible error was from
weighing of the electrodes. The electrode must be dried completely before being weighed. The
contribution from electrolyte might have caused the cathode to gain phantom mass.

The charge effect efficiency was found to be 88.11% and 71.03% for trial 1 and trial 2
respectively. and the calculation is shown as the following:

m = (M x Q)/nF

where m is the mass of metal deposited , M is the molecular weight, Q(Q = It) is the coulumbs, n
is the number of electrons and F is the Faraday’s constant.

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Trial 1:
At anode, 0.0467g = (63.54 g/mol x Q)/(2e x 96500 C/mol)
Qa = 141.85 C

At cathode, 0.053g = (63.54 g/mol x Q)/(2e x 96500 C/mol)

Qc = 160.99 C

Charge passed efficiency, Qa/Qc x 100% = 88.11%

Trial 2:
At anode, 0.0385g = (63.54 g/mol x Q)/(2e x 96500 C/mol)
Qa = 116.94 C

At cathode, 0.0542g = (63.54 g/mol x Q)/(2e x 96500 C/mol)

Qc = 164.63 C

Charge passed efficiency, Qa/Qc x 100% = 71.03%

Several errors might have occured in setting up the circuit and experimentally, the presenceof
resistance might have reduced the efficiency.

Conclusion:
As short, both trial 1 and trial 2 have quite high charge passed efficiency. The experiment was
conducted correctly as in the instruction but the measured avogadro’s number for trial 1 and trial
2 were different from actual avogadro’s number.

References:

PHYWE (n.d.) Electrogravimetric determination of copper. Retrieved from:

http://www.phywe.com/index.php/fuseaction/download/lrm-
_file/versuchsanleitungen/P3062201/e/P3062201.pdf. [Accessed 22/10/2013]

University of Wroclaw. (n.d.) Electrogravimeteric Determination of Copper In Alloys. Faculty of

Chemistry, University of Wroclaw, Analytical Chemistry Dept., electrogravimetry. Task 17 –
p. 3

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