Conductance of Aqueous Ions

Purpose
Ionic conductivities of several strong electrolytes will be measured. Limiting ionic conductivities
of the electrolytes’ cations will be calculated.
Introduction
The conductance of a solution, G, is
the inverse of its resistance. A
conductivity meter and cell measure
conductance. At right is a picture of
a conductivity meter and cell
manufactured by Control Company.
The meter has multiple ranges from
microSiemens to Siemens. Range is
selected automatically. In the cell are
two platinum squares between which
conductance is measured.

Conductance, G, is measured in
“Siemens,” S. One Siemen is one
reciprocal ohm. An older name for Siemen is “mho.” Conductivity,
(“kappa”), is conductance
corrected for the geometry of the cell.

=GK (1)
-1
where K is the “cell constant.” The cell constant has units of cm and is basically a scale factor
that accounts for the electrode areas (A) and the distance between the electrodes (L). You will
measure K by measuring the conductance of a 0.0200 M KCl solution at 25ºC, for which the
conductivity is known to be
=0.002768 S/cm. Then

0.002768 S / cm
K= = . (2)
G your measured G
One must not confuse K, the cell constant, with
, the conductivity. Conductivity is
approximately proportional to concentration, c. The ratio is called the “molar conductivity,” .
Molar conductivity is ordinarily expressed in S·cm2/mol. In those units, and with c in mol/L and

in S/cm,

= (1000 cm3/L) ×
/c . (3)

As concentration goes to zero,  approaches 0. The Debye-Huckel-Onsager equation (see

Engel and Reid1, equation 17.73, page 444) is
 = 0 -  (c /1M)1/2 (4)
1/2
where  is a constant slope of a graph of  versus c . 0 is the intercept.

Conductivity.odt 1
The limiting molar conductivity, 0, is approximately the sum of limiting ionic conductivities of
the ions in the solution. For a simple 1:1 electrolyte C+A- (which dissociates into two ions, C+
and A-):
0 = C+ + A- (5)

Ionic conductivities are related to sizes of ions. Combining the Nernst-Einstein equation for the
diffusion constant [ D=RT/(F2|z|) , Laidler’s2 equation 19.73] and the Stokes-Einstein equation
[D=kT/(6r), Engel and Reid,1 equation 17.53, Laidler’s2 equation 19.77] leads to Stokes’
equation (Robinson and Stokes3, equation 2.49) for the hydrodynamic radius:
r = e F / ( 6  Me+) (6)
In the equation for r, e is the electron charge, F is the Faraday constant, and  is the viscosity
of water (0.891×10-3Pa·s). (The subscript "Me+" stands for the cation of a metal, not for
"methyl.")

The Stokes formula is an approximate formula for the effective radius of an ion and its
associated water molecules as it moves through water: hence the “hydrodynamic” radius. An ion
with a high charge density tends to bind more solvent water molecules and bind them more
tightly than an ion with lower charge density, so ions that are smaller in the gas phase may have
larger hydrodynamic radii. Atkins and dePaula4 discuss the idea in Section 21.7. Ladd5 discusses
the matter at greater length and gives a more accurate estimate of radii.

The limiting (infinite dilution) molar conductivity of a strong electrolyte is the intercept of a 
versus c1/2 plot, as shown by equation 4. This graphical limit cannot be used to find 0 for weak
electrolytes such as acetic acid (CH3COOH), because for a weak electrolyte a plot of  vs. c1/2 is
steep in the low concentration range, making extrapolation difficult. In such a case, 0 may be
calculated by adding limiting conductivities of individual ions. In this experiment the limiting
molar conductivity of acetic acid will be calculated by combining conductivities of the three
strong electrolytes NaCl, HCl and NaCH3CO2.
0(HCH3CO2) = H+ + CH3CO2- = H+ + Cl- - (Na+ + Cl-) + (Na+ + CH3CO2-)
In terms of the results of this experiment:

0(HCH3CO2) = 0(HCl) - 0(NaCl) + 0(NaCH3CO2) (7)

Conductivity.odt 2
Reagents
Solids make formula mass grams
LiCl 100 mL 0.100 M 42.39 g/mol 0.424
NaCl 100 mL 0.100 M 58.44 g/mol 0.584
NaCH3CO2 or 100 mL 0.100 M 82.03 anhydrous or 0.820 or
NaCH3CO23H2O 136.08 g/mol trihydrate 1.361
Note that sodium acetate and sodium acetate trihydrate yield the same ions when dissolved in water,
so it does not matter which is used, except that different masses are required.
KCl 500 mL 0.0200 M 74.55 g/mol 0.746
Solution already made
HCl 0.100 M

Supplies
1 500-mL volumetric flask
4 100-mL volumetric flasks
100 mL transfer pipets
automatic pipet is in the lab for 1-mL samples
pipet bulb
200-mL conductivity beaker (tall, narrow beaker)

Procedure
Take all conductance measurements with the sample in a 200-mL conductivity beaker in a water
bath at 25ºC. Temperature strongly affects conductivity, so be sure solutions have reached the
bath temperature before reading conductance. Steady upward drift of conductance suggests
temperature is still rising. Keep the cell in the middle of the beaker; it should be 5 mm or more
from any other surface. Turn on the magnetic stirrer that is immersed in the water bath. Position
the cell above and close to the stir bar.

Ideally, all solutions should be made up using conductivity water, which is water free of
dissolved ions and gases. We will use distilled water. Distilled water has some small
conductance, Gwater. Measure the conductance of the distilled water, which should be less than
10 S. Subtract Gwater from all conductances you measure.

Make up 500 mL of 0.0200 M KCl by dissolving solid KCl in distilled water. Measure the
conductance of 0.0200 M KCl three times, and use the average (minus Gwater) to calculate the
cell constant, K. For exactly 0.0200 M KCl,
=0.002768 S/cm. If your KCl concentration differs
from 0.0200 M (based on the mass of KCl you dissolved) correct
proportionately. Then use
your average GKCl and the known KCl
and equation 2 to calculate the cell constant, K. You will
use K to convert conductances of all other solutions to conductivities.

Conductivity.odt 3
Prepare 0.10 M solutions of LiCl, NaCl and NaCH3CO2. It is necessary to know the exact
concentration of each solution, but it is not necessary that they equal 0.1 exactly. Actual
concentrations are used in the calculations, whether exactly 0.1 or not.

Measure the conductance of LiCl as a function of concentration, as follows.

1. Pipet (use a transfer pipet) 100 mL distilled water into a clean dry 200-mL conductivity
beaker in the water bath. Stir. Wait for temperature equilibration (about 3-5 minutes).
Measure the conductance. It should approximately equal the Gwater you measured earlier.

2. Pipet in 1 mL of 0.1 M LiCl. An automatic pipetter is best, but a glass transfer pipet will
also serve. Wait for stirring and temperature equilibration. Record the conductance.

3. Pipet additional volumes of 1, 2, 2, 2, and 2 mL of 0.1 M LiCl, recording the conductance

after each addition.

4. Remove the cell from the bath. Clean and dry the cell.

In the same way, measure the conductances of NaCl, HCl and NaCH3CO2 as functions of
concentration.

The solutions are sufficiently dilute that volumes are additive. Calculate and tabulate total
volume (mL) and concentration (mM).

electrolyte
concentration, with
Solutio Add volume of Total volume cstock
0.1 being the
n 0.1 M electrolyte (mL) molarity of the stock.
water none 100 0
A 1 101 cstock ×1/101
B 1 102 cstock ×2/102
C 2 104 cstock ×4/104
D 2 etc etc.
E 2
F 2

At the end of the experiment please rinse the conductivity cell in distilled water, then leave it
suspended in air to dry.

Conductivity.odt 4
Calculations and Report
Report the conductance of the distilled water.

Report the conductances of three samples of 0.0200 M KCl, their average conductance, and the
cell constant.

Make a table of G,
, and  for all LiCl, NaCl, HCl and NaCH3CO2 concentrations.

Graph  versus c1/2 for all four electrolytes. Show your data points and your trend lines. Use
Excel’s regression analysis to calculate intercepts (0) and their uncertainties. Make a table of
your 0 values for all electrolytes. Literature values of 0 are available, for example, in
Shedlovsky’s 1932 article6 and more readily in the CRC Handbook of Chemistry and Physics.7

Using a literature value of the limiting ionic conductivity of the chloride ion, °Cl-, calculate the
limiting ionic conductivities of Li+ and Na+. For example, ºLi+ = 0(LiCl) - ºCl-.

Use Stokes’ formula (equation 5) and your limiting ionic conductivities to calculate
hydrodynamic radii of Li+ and Na+. For those two ions, make a table including o, literature
values of o, percent errors in o, your calculated hydrodynamic radii, and ionic (i.e., crystal)
radii. Crystal radii are often given in General Chemistry textbooks. You can also find ionic radii
in “webelements” on the web.8 Explain the order of the hydrodynamic and crystal radii of
lithium and sodium ions.

Calculate 0 for acetic acid using o values you found for NaCl, HCl and sodium acetate.
Compare your result with the literature (e.g., CRC Handbook7) value. When looking for a
literature value for 0(acetic acid), bear in mind that 0(HCH3CO2) = ºH+ + ºCH3CO2-.

Conductivity.odt 5
References
1. Engel, T.; Reid, P. Thermodynamics, Statistical Thermodynamics and Kinetics, Pearson
Benjamin Cummings, San Francisco, 2006.
2. Laidler, K. J.; Meiser J. H.; Sanctuary, B. C. Physical Chemistry, Fourth edition, Houghton
Mifflin Company: Boston, 2003. Chapter 7.
3. Robinson R. A. and Stokes R. H. Electrolyte Solutions, Second edition, Butterworths, 1968.
4. Atkins P. W., DePaula, J. Physical Chemistry, Eighth edition, Freeman, 2006.
5. Ladd M. Introduction to Physical Chemistry, Third Edition, Cambridge University Press,
1998. chapter 9.
6. Shedlovsky T. (1932) “The electrolytic conductivity of some uni-univalent electrolytes in
water at 25°C,” Journal of the American Chemical Society 1932, 54, 1411-1428.
7. Handbook of Chemistry and Physics; 71st ed; Lide, D. W., ed.; CRC Press: Boca Raton,
1990, pages 5-97 and 5-98.
8. Webelements ionic radii. The site for Li is analogous.
http://www.webelements.com/webelements/elements/text/Na/radii.html
9. Kohlrausch F. W. and Grotrian O. N. A. (1875) “Das elektrische Leitungsvermogen der
Chlor-Alkalien und alkalinischen Erden, sowie der Salpetersaure in wasserigen Losungen,”
Nachr. Ges. Wiss. Gottingen, 405-408, 1874, Poggendorff’s Ann. der Phys. und Chem. 154,
1-14, 215-239. English translation “The electrical conductivity of alkali chlorides, alkaline
earth chlorides and nitric acid in aqueous solutions,” Phil. Mag.,1875, 49, 417-425.

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