ION-ECR

Ion Mobility: Transference Number of Ions

Analysis of Electrochemical Reactions

Dates of the Experiment

7-17-2014
8-292014
10-32014

8-30-2014
9-112014

10-112014

Objectives

ION
1. To determine the transference numbers of nitrate and
hydronium ions
2. To discuss the effect of mass on the transference
number of an ion

Objectives

ECR
1. To describe the reactions that occur in the cathode
and anode regions of the transference vessel and
copper coulometer
2. To analyze the thermodynamic properties and material
balance of the electrochemical reactions

Theoretical Background
Electrochemistry is the study of the interchange of
chemical and electrical energy.
It is concerned with processes that involve redox
reactions:
The generation of an electric current from a
spontaneous chemical reaction
The use of a current to produce chemical change
ION-ECR

Theoretical Background
An electrochemical cell is a device capable of either
generating electrical energy from chemical reactions or
facilitating chemical reactions through the introduction
of electrical energy.
Galvanic/voltaic cell
Electrolytic cell
It consists of two electrodes, or metallic conductors, in
contact with an electrolyte, an ionic conductor (which
may be a solution, a liquid or a solid.

ION-ECR

The Electrolytic Cell

power source provides electrical
current and is responsible for the
charges of electrodes

electrodes conductors used to

establish electrical contact with a
nonmetallic part of a circuit

electrolyte is the ionic

compound in its molten or
aqueous state. It provides
mobile electrons that allow
electrical conduction

cathode the negatively charged

electrode, it attracts cations,
where reduction takes place

anode the positively charged

electrode, it attracts anions,
where oxidation takes place

ION-ECR

The Experimental Set-up

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ee-

e-

e-

e-

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The Coulometer
The reactions:
Anode:

Cu(s) Cu2+(aq) + 2e-

Cathode:

Cu2+(aq) + 2e- Cu(s)

Useful parameter:

ION-ECR

The Transference Vessel

Observations:

Formation of bubbles
Concentration of
HNO3
Disintegration of the
carbon electrode

Anode

Cathode

present

present

increased

decreased

present

absent

ION-ECR

The Transference Vessel

The reactions:
Anode:
Cathode:

3H2O 6H+ +3/2 O2 (g)+ 6e6H+ + 6e- 3H2 (g)

Net:

3H20 3H2

(g)

+3/2 O2 (g)

Useful parameter:

ION-ECR

The Transference Number

It is the fraction of the total current that is carried by the ion

Also called transport number
Hittorf transference numbers are experimentally obtainable through resulting
characteristic changes that occur in the cathode and anode of an electrochemical
cell
Related to current transport, charge transport, ion mobilities, ionic conductivities
If cationic species have higher ion mobility, more of these species are transported
from the anode to the cathode region whereas in the same period, less anionic
species are transported from the cathode to the anode area

ION-ECR

The Gibbs Free Energy of Reaction

A negative value would indicate spontaneity

A positive value would indicate non-spontaneity

ION-ECR

Data and Results

T=27C
Group Code

t-

t+

t+/t-

ChE412L01THURS

0.255776

0.74422351

2.909663

ChE412L06THURS

0.277374

0.72262597

2.60524

ChE412L07THURS

0.408125

0.59187486

1.450229

MEAN

0.313759

0.68624145

2.321711

Standard Dev

0.828397

0.06730727

0.628638

Data and Results

T=28C
Group Code

t-

t+

t+/t-

ChE412L02THURS

0.193832

0.80616816

4.159111

ChE412L03THURS

0.172549

0.82745112

4.795459

ChE412L04THURS

0.152248

0.84775198

5.56823

ChE412L05THURS

0.254927

0.74507299

2.922691

MEAN

0.193389

0.80661106

4.361373

Standard Dev

0.038451

0.03845131

0.968975

Data and Results

T=27C
Group Code

qed [C]

qmd [C]

Ged

Gmd

Percent
difference (%)

ChE412L01THURS

271.0368

271.2

333.3753

333.576

0.06016696

ChE412L06THURS

228.9768

253.7256

281.64143

312.0825

9.75417122

ChE412L07THURS

269.3666

270.75

331.32088

333.0225

0.51096132

MEAN

256.4601

265.2252

315.44587

326.227

standard dev

19.44558

8.133520153

23.91805976

8.663917

Data and Results

T=28C
Group Code

qed [C]

qmd [C]

Ged

Gmd

Percent
difference (%)

ChE412L02THURS

269.5184

264.6

331.50765

325.458

1.85881088

ChE412L03THURS

276.1994

270

339.7253

332.1

2.29608645

ChE412L04THURS

331.4697

261.6

407.70772

321.768

26.7085965

ChE412L05THURS

271.796

271.2

334.30912

333.576

0.21977655

MEAN

287.2459

266.85

353.31245

328.2255

standard dev

25.64532

3.920140304

31.54374519

4.8217726

Data and Results

TEMPERATURE C

t-

t+

t+/t-

25

0.17

0.83

27

0.3138

0.68624

2.321

28

0.1934

0.80661106

4.361

TEMPERATURE
C

qed [C]

qmd [C]

Ged

Gmd

27

256.46

265.2252

315.446

326.227

28

287.246

266.85

353.312

328.2255

Statistical Treatment
At the temperature 27 degrees Celsius, by inspection, the t- value =
0.408125 is hypothesized to be an outlier. To confirm this, we used the
Q Test for a 3 value range.
Q Test:
Qexp = = = 0.8582
From Qcrit Table.
0.970 0.8582
Qcrit
The value is not an
OUTLIER at 95%
Confidence Level

Statistical Treatment
the temperature 28 degrees Celsius, the same procedure was done
At
to check if
t- value = 0.254927

Q Test:
Qexp = = = 0.5951
From Qcrit Table.
0.970 0.5951
Qcrit

The value is not an

OUTLIER at 95%
Confidence Level

Conclusion
The transference number cannot be measured directly by any device. In the
experiment, it was experimentally determined by the change in masses of the
copper electrodes and the concentration changes in the two compartments of the
transference vessel.
Generally, the transference number of hydronium ions is greater than that of
nitrate ions. From Hittorfs Rule we can infer that the hydronium ions are faster.
Theoretically, at T=25C, the hydronium ion is almost 5 times faster than the
nitrate ions.
This may be attributed to the difference in masses between the two ions, nitrate is
relatively heavier than the hydronium ion.
Redox reactions are happening in both the copper coulometer and the transference
vessel. In the former the reduction of Cu2+ ions to Cu and the latter the hydrolysis
of water.
The power source drives these otherwise nonspontaneous reactions to spontaneity.
This was verified by calculating the of the reaction, which were positive.

ION-ECR