Laboratory Experiment

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Determining the Transference Number of H+(aq) by a Modified

Moving Boundary Method: A Directed Study for the Undergraduate
Physical Chemistry Laboratory
Rajeev B. Dabke,* Zewdu Gebeyehu, and Jonathan Padelford
Department of Chemistry, Columbus State University, Columbus, Georgia 31907, United States
*
S Supporting Information
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ABSTRACT: A directed study for the undergraduate physical chemistry laboratory for determining the
transference number of H+(aq) using a modified moving boundary method is presented. The laboratory
study combines Faraday’s laws of electrolysis with mole ratios and the perfect gas equation. The volume
of hydrogen gas produced at the cathode is monitored and the perfect gas equation is applied to
determine the amount of H2(g) produced. The transference number of H+(aq) is then determined from
Publication Date (Web): September 26, 2012 | doi: 10.1021/ed200786a

the volume of HCl(aq) swept by the boundary, the molarity of HCl(aq), and the amount of H2(g)
produced. The cell is directly powered by 9 V batteries and involves no electronic circuit or a
milliammeter. Preparation of the electrochemical cell, experimental procedure, and results of the
experiment are presented.

KEYWORDS: Upper-Division Undergraduate, Laboratory Instruction, Physical Chemistry, Hands-On Learning/Manipulatives,

Electrochemistry, Electrolytic/Galvanic Cells/Potentials

T ransference number (or transport number) is one way of

expressing conductivity and mobility of ions1 and
determining the junction potential in an electrochemical
cell.2,3 The theory of transference number and the methods
for measuring it are known to physical chemists and
electrochemists.1−6 Various reports on determining the trans-
ference number of ions as a laboratory experiment and the
pedagogical values of these experiments have appeared in this
Journal7−20 over several decades. These reports include the
moving boundary method,8,11,15−19 the Hittorf method,7,13,14,20
and the electromotive force method.10 In particular, the moving
boundary method8,11,15−19,21 has been at the forefront for the
determination of transference numbers of ions. The volume of
electrolyte swept by the boundary may be measured with more
accuracy than the change in concentration of an ion in the
Hittorf method.21
Transference number can be defined as a fraction of total
current carried by each ion present in solution. The moving
boundary apparatus consists of a graduated pipet filled with the
desired electrolyte and the electrodes are positioned at the
upper and lower end of the pipet serving as a capillary. A direct
current is passed through the electrodes. For determining the
transference number of H+(aq), the capillary is filled with
aqueous hydrochloric acid of known concentration and methyl
orange as a visual indicator. Passage of direct current prompts
migration of H+(aq) toward the negative electrode (cathode).
As H+(aq) ions are swept away from the anode, a moving
boundary is formed. The red coloration above the boundary
indicates the presence of H+(aq). The lower yellow coloration
© 2012 American Chemical Society and
Division of Chemical Education, Inc.
indicates the absence of H+(aq). Measuring the volume of acid
swept by the boundary per unit time and the current facilitates
the determination of the transference number of H+(aq) from
eq 1.6
z+clAF
t+ =
I Δt (1)
where t+ is the transference number, z+ represents charge on
the H+ ion (i.e., +1), c is molar concentration of H+(aq), F is
the Faraday constant (i.e., 96485.3 C mol−1), I is current in
ampere, and Δt is time in seconds, respectively. In a capillary,
the moving boundary sweeps a volume (L or dm3) of HCl(aq)
in the form of a cylindrical shape of height l dm and the cross-
sectional area of A dm2. Hence, the term lA in eq 1 represents
the volume of HCl(aq) swept by the moving boundary.
Dimensional analysis of eq 1 indicates that transference number
is a dimensionless quantity. As indicated in eq 1, transference
number can be determined from the rate of migration of the
boundary at a known current. The current tends to gradually
decrease during movement of the boundary.11,17 Nevertheless,
in view of applying eq 1, it is critically important to maintain a
constant direct current during the experiment. This stringent
condition demands a constant manual adjustment of the
current11,16,18,19 or construction of a constant current
supply.15,22
In this paper, we present a modified moving boundary
apparatus. The apparatus directly runs on 9 V batteries and
Published: September 26, 2012
1600 dx.doi.org/10.1021/ed200786a | J. Chem. Educ. 2012, 89, 1600−1603
 Journal of Chemical Education
does not involve a milliammeter, rheostat, or an electronic
circuit to regulate the current. The term IΔt in eq 1 is a product
of the current (amp) and the time (s) and it represents the
charge (coulombs) passed through the electrochemical cell.
The charge passed through the cell quantitatively accounts for
the volume of HCl(aq) swept by the moving boundary. A 2 mL
graduated pipet serves as a capillary and measures the volume
of HCl(aq) swept by the boundary. The volume of H2(g) is
measured and the perfect gas equation is used to determine the
amount of H2(g). Equation 2 shows the reduction of H+(aq) to
H2(g) at the cathode.
2H+(aq) + 2e− → H 2(g) (2)
Faraday’s laws of electrolysis and eq 2 point out that two
Faradays of charge delivers 1 mol of H2(g). The quantity of
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charge (IΔt) passing through the electrochemical cell is
calculated from these relations and eq 1 is used to determine
the transference number of H+(aq).
The apparatus used in the present experiment is comprised
of a cadmium anode and a platinum cathode (Figure 1). As the
Publication Date (Web): September 26, 2012 | doi: 10.1021/ed200786a
power supply is started, a boundary is started at the anode and
moves in the upward direction. The H2(g) is evolved at the
Figure 1. Schematic diagram of the transference number cell: (a) three
9 V batteries connected in series, (b) platinum wire electrode, (c)
hydrogen gas bubbles produced at the platinum electrode, (d) ) 5 mL
glass pipet holding HCl(aq), (e) HCl(aq) level, (f) three magnetic stir
bars, (g) Parafilm seal, (h) the height of the aqueous electrolyte
column, (i) HCl(aq) electrolyte, (j) boundary formed in the capillary,
(k) yellow coloration of methyl orange indicating the absence of
H+(aq) ions, (l) cadmium metal electrode housed in the capillary, (m)
switch, and (n) water jacket. Note: A large magnetic stir bar is taped to
the pipet, serving as a docking station for the small magnetic stir bar
housed inside the pipet. The small magnetic stir bar is moved in the up
and down direction through the pipet to dislodge the hydrogen gas
bubbles adhering to the inner surface of the pipet. The small magnetic
stir bar is guided by the manual movement of another large magnetic
stir bar. Dashed arrow shows the movement of the large magnetic stir
bar.
1601
Laboratory Experiment
cathode. In a separate experiment a milliammeter is included in
the circuit. During the progress of this experiment, the current
gradually decreases. This resulted in a gradually decelerating
migration of the boundary and production of H2(g). However,
Faraday’s laws of electrolysis confirm the quantitative relation
between the amount of H2(g) produced at the cathode and the
charge passing through the electrochemical cell, irrespective of
both the speed of the movement of the boundary or the speed
of the production of H2(g). Relatively simple circuitry, colorful
change in the capillary, and the application of Faraday’s laws of
electrolysis combined with the mole ratios and the perfect gas
equation make this experiment suitable for a directed study in
undergraduate physical chemistry laboratory. A student
developed and tested this experiment as a fourth-year research
project in our physical chemistry laboratory.
■
PEDAGOGICAL OBJECTIVES
The pedagogical objectives of this experiment are (i) to apply
the perfect gas equation to determine the amount of a gas
produced at the electrode, (ii) to apply the mole relationships
to quantify the electric charge passed through an electro-
chemical cell, (iii) to apply Faraday’s laws of electrolysis, and
(iv) to determine the transference number of H+(aq).
■ EXPERIMENTAL SETUP
The moving boundary cell (Figure 1) is made of a PTFE
(polytetrafluoroethylene) beaker and two pipets. The cadmium
electrode is positioned at the base of the 2 mL graduated pipet
that serves as a capillary. A 20 mL portion of HCl(aq) of
known concentration with indicator is placed in the cell which
is powered by three 9 V batteries connected in series. An
upward moving boundary is formed in the capillary. An
inverted glass pipet (5 mL capacity) is used to measure the
volume of hydrogen gas produced at the cathode. The volume
of HCl(aq) swept by the moving boundary and the volume of
the H2(g) produced at the platinum electrode are recorded.
The average height of the electrolyte column in the gas
measuring pipet is measured to determine the contribution of
the hydrostatic pressure. A complete description of exper-
imental procedures, instructions for the staff and students, step-
by-step calculations, and a postlaboratory exercise are included
in the Supporting Information.
■ HAZARDS
Safety glasses must be worn while performing the experiment
and instructors must examine and approve the electrode
connections before students begin the experiment. Hydrogen
gas is flammable and a fume hood or a workstation with a
proper exhaust system must be used for a large size class.
Hydrochloric acid causes burns, is harmful if inhaled, and must
be prepared in a fume hood. Cadmium metal serving as an
anode slowly dissolves in the acid. Cadmium metal is harmful if
swallowed and chronic inhalation of cadmium compounds has
been associated with lung and prostate cancer. Labeled waste
containers must be used to collect the waste chemicals.
■ RESULTS AND DISCUSSION
The pressure of gas collected in the empty space in the pipet is
corrected for the vapor pressure of water and for the
hydrostatic pressure of the electrolyte column.23,24 Table 1
provides data on five independent trials of determination of
transference number of H+(aq). Battery current is stopped and
dx.doi.org/10.1021/ed200786a | J. Chem. Educ. 2012, 89, 1600−1603
 Journal of Chemical Education Laboratory Experiment

Table 1. Experimental Data and Results for Determination of Transference Number of H+(aq)
Trial Molarity of Barometer Volume of H2(g) Volume of HCl(aq) swept by Average Height of the Transference
Numbera HCl(aq)/M Pressure/mm Hg Produced/mL boundary/mL Electrolyte Column/cm Numberb
1 0.105 758.2 0.50 0.31 7.0 0.82
2 0.107 758.2 0.50 0.31 10.8 0.84
3 0.100 753.2 0.20 0.13 12.0 0.83
4 0.100 753.2 0.20 0.13 11.0 0.82
5 0.100 753.2 0.20 0.13 10.5 0.82
a
The temperature was 22.0 °C. The density and vapor pressure of water at this temperature are 998 kg m−3 and 19.8 mm of Hg (or 0.0261 atm),
respectively.23 bTransference number from the average of five trials =0.83 (standard deviation ±0.01)

the electrolyte is changed after each trial. The average
transference number of H+(aq) is determined to be 0.83
(standard deviation ±0.01).
In a separate experiment, the volume of H2(g) produced at
the cathode is monitored as a function of the volume of
the migration of the boundary through 0.80 mL volume. The
temperature of HCl(aq) is measured before and after each trial
and no measurable change in the temperature is noticed. The
hydrogen gas produced in the experiment is treated as a
“perfect” gas for calculations.

■
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HCl(aq) swept by the moving boundary. The volume of H2(g)

produced linearly changed with the volume of HCl(aq) swept
by the moving boundary. The data for two different
concentrations of HCl(aq) are plotted (Figure 2). This linear
Publication Date (Web): September 26, 2012 | doi: 10.1021/ed200786a
CONCLUSION
The agreement between the transference number value within
experimental results and that between experimental results and
the literature data1,3 (Table 2) underlines the efficacy of the

Table 2. Summary of Experimental Results and Literature

Data for Transference Number of H+(aq) by Moving
Boundary Method
Transference
Source Number Value
Experimental
Average of 5 Trials HCl (0.102 M HCl average 0.83
concentration) at 22.0 °C from Table1
Figure 2: 0.100 M HCl at 22.0 °C 0.83
Figure 2: 0.195 M HCl at 22.0 °C 0.84
Literature
0.10 M HCl at 25 °C 0.8314a
0.20 M HCl at 25 °C 0.8337a
Figure 2. Plot of volume of H2(g) produced at cathode versus volume a
Refs 1, 3.
of HCl(aq) swept by the moving boundary. The electrolyte
temperature was 22.0 °C; barometric pressure was 756.5 mmHg.
Average height of the electrolyte column was 12.1 and 10.5 cm for
0.100 and 0.195 M HCl, respectively. The density and vapor pressure modified moving boundary experiment. The transference
of water at 22.0 °C temperature are 998 kg m−3 and 19.8 mm of Hg, number of H+(aq) does not significantly depend on the
respectively.23 The derivation justifying these plots is discussed in the concentration of HCl(aq) in 0.10 to 0.20 M range1,3 and our
Supporting Information. data support this observation. Equation 1 contains concen-
tration c in units of mol/L, which is slightly temperature
dependence confirmed the quantitative relation between the dependent through the density of water. This relation indicates
amount of the products generated at the cathode and the the transference number is slightly dependent on temperature.
volume swept by the moving boundary. The slope of the plot Application of the perfect gas equation and Faraday’s laws of
for 0.100 M HCl(aq) is 1.53 (R2 = 0.998). The slope signifies electrolysis encompass the undergraduate physical chemistry
pedagogy and address the objectives of the study.

■
1.53 mL of H2(g) produced at the cathode accounts for a unit
volume (i.e., 1.0 mL) of HCl(aq) swept by the moving
boundary. The transference number for 0.100 M HCl is ASSOCIATED CONTENT
determined to be 0.83. The experiment is repeated for the *
S Supporting Information
higher concentration of HCl(aq) and slope of the plot for 0.195 A complete description of experimental procedures; instruc-
M HCl(aq) is higher than that for 0.100 M HCl by a factor of tions for the staff and students; step-by-step calculations; and a
1.92 (Figure 2). This is nearly the value 1.95 expected from the post-laboratory exercise. This material is available via the
concentrations. The transference number of H+(aq) for 0.195 Internet at http://pubs.acs.org.
M HCl is 0.84.
The significant figures in the transference number
determined from our experimental data are limited by the
■ AUTHOR INFORMATION
Corresponding Author
digits in the measured volume of H2(g). In a separate
*E-mail: dabke_rajeev@columbusstate.edu.
experiment, we monitored the current flowing through the
circuit during the progress of the experiment. The initial Notes
current is 6 mA and gradually dropped to about 1 mA during The authors declare no competing financial interest.
1602 dx.doi.org/10.1021/ed200786a | J. Chem. Educ. 2012, 89, 1600−1603
 Journal of Chemical Education

■
Laboratory Experiment

ACKNOWLEDGMENTS
Jonathan Padelford was the fourth-year undergraduate student
testing the experiment. We thank James O. Schreck and the
reviewers of the manuscript for their helpful comments and
suggestions.

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