EXPERIMENT 10: CONDUCTIMETRY

Natorilla, Haziel May C.

Mendoza, Enrico

Chem 157.1 - DE
Mr. Leonardo Dante P. Yambot

Department of Physical Sciences and Mathematics

College of Arts and Sciences
University of the Philippines Manila
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Theoretical Framework

The flow of electricity through a conductor involves the transfer of electrons from a
point of higher negative potential to one of lower negative potential. Transfer can be done
through electronic conductors (conduction takes place via direct migration of electrons
through the conductor), or by electrolytic conductors (conduction takes place via migration of
ions, both positive and negative, towards the electrodes). Upon placing an electric field across
an aqueous solution (that is, by applying a voltage between two parallel plate electrodes), the
cations are attracted towards the negative plate (cathode) and the anions towards the positive
plate (anode).

Electrolyte solutions obey Ohm’s law. If a wire is placed between the two terminals of
a battery and the circuit is closed, current will flow. The amount of current which flows
depends on the resistance of the wire according to Ohm’s law,
V=IR (1)
where V is the voltage, I the current, and R the resistance of the wire.
This resistance will depend on the composition of the wire and on its geometry.

It is possible to characterize a material by measuring an intrinsic property of the

material called resistivity, ρ. The relationship between the resistance of a material and the
geometric independent resistivity is:

ρ = R A/L (2)
Often, we discuss the conductivity, κ, instead of the resistivity. Conductivity is the
inverse of the resistivity,

κ= 1/ρ (3)

The conductance of all electrolytes increases with increasing temperature.

Conductivity, the absolute velocity of an ion moving through a solution (which is dependent
on: type and concentration of ions present, solvent, area of electrode, and distance between
the electrodes) can be measured with a conductivity meter.
 If the solvent is pure water, there are only few charged species (ions) present. K w
=[OH-][H+]=10-14, and the conductivity measured will be low. For instance, the addition of ions
such as in a 0.10 N solution of NaCl (Λ = 106.8 Ω -1 cm2 mol-1) will increase the conductivity of
the solution to 106.8 Ω-1cm2mol-1x 0.01mol/1000 cm3 = 10.68 x 10-6Ω-1 cm-1 or 1068 x 10-6Ω-1
m-1.

According to Kohlrausch’s Law of Independent Migration for Infinite Dilution, the

molar conductivity varied as the square root of the concentration for many solutions.

Λ m = Λmo - k c1/2 (4)

where the limiting molar conductivity at infinite dilution, Λmo , is a constant which
depends on the electrolyte. The constant, k, is more dependent on stoichiometry of the
electrolyte than its nature. The difference in Λo for pairs of salts with a common ion is
expected to be the same regardless of the common ion.

The molar conductivities at infinite dilution can be used to determine conductivity at

infinite dilution for individual ions to yield the law of the independent migration of ions. For
instance, the limiting conductivity of NaCl could be determined by the relationship:

ΛoNaCl = Λ oNa+ + Λ oCl- (5)

Now, the increase of the equivalent conductance of solutions of strong electrolytes in

the low-concentration range is not associated to an increase in dissociation (because the
dissociation is complete), but rather, it is associated to an increased mobility of the ions. In a
concentrated solution of a highly ionized strong electrolyte, the ions are close enough to one
another so that any one of them in moving is influenced not only by the electrical field
impressed across the electrodes but also by the field of the surrounding ions. The ionic
velocities are, then, dependent upon both forces.

On the other hand, some electrolytes (weak electrolytes) do not dissociate completely
in solution. Instead, equilibrium exists between ions and associated electrolyte. The apparent
equilibrium constant for dissociation may be calculated as

α 2c2
K=
(1 − α )c
(6)
where α = degree of dissociation, and c = concentration of the solute.
 Conductance measurements can be used to determine the solubility of difficultly
soluble substances, and the ionization constant for a weak electrolyte and for conductimetric
titrations. By using the equation λm = 1000 Ls / C, C being the concentration of substance, its
solubility can be calculated. To find the degree of ionization α, λm and λ0 are required.
According to the Arrhenius theory, the equivalent conductance at any concentration is related
to the degree of dissociation by:
α = Λ/Λo (7)
where Λ = equivalent conductance at concentration c, and Λo = equivalent
conductance at infinite dilution.

In the case of a weak electrolyte the value of Λo cannot be obtained by the

extrapolation to infinite dilution of results obtained at finite concentration, because Λ is a
rapidly varying and nonlinear function of Λc. Instead, Λo is obtained by the law of Kohlrausch
(eqn. 5).

The apparent equilibrium constant Ka, is equal to the true equilibrium constant, which
can be expressed in terms of activities only for ideal solutes (because γ = 1.0).

cH + c R− γ H cH γ R cR
+ + − −
Ka = K =
c HR γ HR c HR
(8)
where γ i is the activity coefficient of species i. Since γ i=1.0 for infinitely dilute solutions,
Lim Ka = K
c 0

Arrhenius noted that the molar conductivities of electrolytes decreased with

increasing concentration. He attributed the decrease in conductivity to the decrease in the
degree of ionization of the electrolyte.

The mobility µ of an ion is defined as the velocity per unit field strength, or µ+ = υ+/E
and is µ -= υ-/E. From Ohm’s law and the definition of conductivity, then κ = I/E, where I is the
current across a unit area and E is the electric field. The specific conductivity of the solution is
Ls = ne(µ+ + µ-) (9)

Hence, molar conductance is then

Λ = Noe(υ+ + υ-)α (10)

where No is the Avogadro number. Since Noe is the charge on a mole of electrons, or
the Faraday constant F, equation 10 can be written as
 Λo = F(µ+ + µ-) (11)

It is here that Arrhenius made the critical assumption that at infinite dilution ionization
is complete, that is, as m =0, a =1. In the limit,

Λ = F(µ+ + µ-)α (12)

and by combining previous we get the expression for the degrees of ionization,

α = Λ /Λo (13)

Methodology

Objectives:
1. To be able to determine the relative mobilities of some ions in solution
2. To be able to determine the molar conductance of different concentrations of
solutions of electrolytes
3. To determine the molar conductance at infinite dilution of an electrolyte
4. To determine the ionization constant of a weak electrolyte by conductance
measurement
5. To be able to determine the concentration of an electrolyte by conductance
measurement

Procedure:

A. Preparation of Conductance Cell

2 holes 1 inch apart in 3” x 3” square cardboard/Styrofoam; Insert electrodes in holes

Put cardboard with electrodes on 50-ml beaker with electrodes1 cm from bottom of beaker

Connect graphite rods in series with 9-V cell and digital multimeter

B. Determination of Relative Ionic Mobility

Prepare: (20 ml of each in 50 ml beaker) 1 M HCl, 1 M NaOH, 1 M NaCl, 1 M NH4Cl and 1 M

NaC2H3O2

Dip electrodes in each solution, measure conductance of each solution; Wash probe and dry
after use

Tabulate in increasing order solutions containing Cl- ; Determine relative mobility of cations.

Do the same for solutions containing Na+

C. Determination of cell constant

Prepare: (In a 50ml beaker) 25 ml 0.100 m KCl (t = 25˚C)

Measure resistance, calculate cell constant.

D. Variation of molar conductance with concentration

Serial Dilution: From 1 M HCl, 25 ml of the following: 0.50 M, 0.20 M, 0.10 M, 0.050 M, 0.020
M and 0.010

Repeat using NaC2H3O2 and NaCl

Measure resistance of each solution at 25˚C; Calculate L, LS, and λm

E. Determination of Ionization Constant of a Weak Electrolyte by Conductance

Measurement

Serial dilution: From 1 M HC2H3O2: 0.20 M, 0.10 M, 0.050 M, 0.020 M, 0.010 M

Measure resistance of each; Calculate LS and λm, α, and Ka of HC2H3O2

F. Determination of Solubility Product Constant by Conductance Measurement

Prepare: (In 50 ml beaker) 12.5 ml 0.05 M Ca(NO3)2 + 12.5 ml 0.10 M

Add NaOH dropwise while swirling

Allow precipitate to form and settle at the bottom of beaker (supernatant = clear)

Measure resistance of solution, calc Ls and λm

G. Conductimetric Titration

25 ml analyte, dip probe and take multimeter reading

+ 1 ml increments slowly while mixing.

Stop reading when multimeter reading no longer shows appreciable change in slope
Results and Discussions

A. Determination of Relative Ionic Mobility

Group 3-4 Group 5-6 Group 7-8
Solution I (A)
Hydrochloric acid 0.757 0.172 0.555
Sodium hydroxide 0.763 0.137 0.142
Sodium chloride 0.760 0.118 0.115
Ammonium chloride 0.750 0.131 0.128
Sodium acetate 0.759 0.096 0.099

A2. Relative Mobility of Cations

Group 3-4 Group 5-6 Group 7-8
Cation I (A)
H+ 0.757 0.172 0.555
Na+ 0.760 0.118 0.115
NH4+ 0.750 0.131 0.128
Relative Mobility: H+ > Na+ > NH4+

A3. Relative Mobility of Anions

Group 3-4 Group 5-6 Group 7-8
Anion I (A)
OH- 0.763 0.137 0.142
Cl- 0.760 0.118 0.115
C2H3O2- 0.759 0.096 0.099
Relative Mobility: OH- > Cl- > C2H3O2-

Ionic mobilities depend largely on the size of the molecule. Since we cannot obtain
the absolute mobilities in this experiment (as we cannot measure the mobility of an anion
separate from the cation), we obtained the relative mobilities. Observed that H + moves fastest
and NH4+ moves the slowest because H+ is a very small particle. For the anions, OH- moves
fastest and acetate ion moves the slowest.

Theoretical values (Absolute Mobilities of Ions at 25°C):

Table -13-10. Maron, Samuel H. and Lando, Jerome B. Fundamentals of Physical Chemistry.

B. Determination of Cell Constant

Group 3-4 Group 5-6 Group 7-8
I (A)
Current of the solution 0.759 0.776 0.076
Resistance of the Solution 11.85770751 Ω 11.59793814 Ω 118.4210526 Ω

Cell Constant 0.152964426 /cm 0.149613402 /cm 1.527631579 /cm

Instead of measuring the resistance, we measured the current, I and solved for K.
Sample Calculations:
Ls KCl = 0.0129 mho/cm at T = 25˚C of 0.100 m KCl

V = I x R, or R = V / I; 9V = 0.776 A x R; R = 11.59793814 Ω
K = R x Ls = 11.59793814 Ω x 0.0129 mho/cm = 0.149613402 /cm

C. Variation of Molar Conductance with Concentration

Sample computations (group 3-4 data):
• Resistance, Ω
R = V / I; = 9V / 0.754 A = 11.780010471 Ω
• Conductance, L
L=1/R = 1 / 11.780010471 Ω = 1.326259947 Ω-1
• Specific conductance, Ls

Ls = K/R or Ls = I (K / V)
Ls = 0.152964426 cm-1 / 11.780010471 Ω = 0.012700617 Ω-1 cm -1
• Molar Conductance, λm

λm = Ls/ C
λm = 0.012700617 Ω-1 cm -1 = 0.012700617 Ω-1 cm -1
1 (mol/L) x (1 L / 1000 cm3) 0.001 mol / cm3
λm = 12.53427835 Ω-1 cm2 mole-1

Group 3-4
M of HCl Current Resistance (Ω) Conductance (Ω-1) Specific Molar
(A) Conductance Conductance
(Ω-1 cm-1) (Ω-1 cm2 mole-1)
1 0.754 12.53427835
11.780010471 1.326259947 0.012700617
0.5 0.752 25.00206185
11.96808511 1.329787234 0.012501031
0.2 0.748 62.17268039
12.03208556 1.336898396 0.012434536
0.1 0.743 123.5141752
12.11305518 1.34589502 0.012351418
0.05 0.732 243.3711339
12.29508197 1.366120219 0.012168557
0.02 0.721 599.2847936
12.48266297 0.080111111 0.011985696
0.01 0.711 1181.945876
12.65822785 0.079 0.011819459

Group 5-6
M of HCl Current Resistance Conductance (Ω-1) Specific Molar
(A) (Ω) Conductance Conductance
(Ω-1 cm-1) (Ω-1 cm2 mole-1)
1 0.239 3.973067009
37.6569038 0.02655556 0.00397307
 0.5 0.210 6.98195876
42.8571429 0.02333333 0.00349098
0.2 0.170 14.13015463
52.9411765 0.01888889 0.00282603
0.1 0.108 17.95360824
83.3333333 0.012 0.00179536
0.05 0.062 20.61340205
145.16129 0.00688889 0.00103067
0.02 0.023 19.11726803
391.304348 0.00255556 0.00038235
0.01 0.011 18.28608247
818.181818 0.00122222 0.00018286

From the results, it can be seen that molar conductance increased as the solution
became more dilute, while the specific conductance decreased as the solution became more
dilute. Theoretically, the molar conductance is expected to increase as the solution becomes
more dilute, while Ls must decrease as the solution becomes more dilute.

group 5-6: HCl

0.25
y = 1.6644x + 0.1137
R2 = 0.118
0.2
molar conductance

0.15
Series1
Linear (Series1)
0.1

0.05

0
0 0.01 0.02 0.03 0.04
square root of C
- all data
group 5-6: HCl
y = 11.365x + 0.0513
R2 = 0.8885
0.25

0.2
molar conductance

0.15
Series1
Linear (Series1)
0.1

0.05

0
0 0.005 0.01 0.015
square root of C
- removed outliers

Y-intercept = 0.0513 = λ0, HCl

 HCl vs measured and expected behavior

25

20
conductance

15
measured
Linear (measured)
10

0
0 0.2 0.4 0.6 0.8 1 1.2
y = -16.865x + 18.966
[HCl]
R2 = 0.8993

The linear equation for this graph is the expected behaviour of HCl, because this is a strong
acid.

Group 5-6
M of NaOAc Current Resistance (Ω) Conductance (Ω-1) Specific Molar
(A) Conductance Conductance
(Ω-1 cm-1) (Ω-1 cm2 mole-1)
1 0.178 2.95902062
50.5618 0.019778 0.002959
0.5 0.15 4.9871134
60 0.016667 0.002494
0.2 0.083 6.8988402
108.4337 0.009222 0.00138
0.1 0.047 7.81314433
191.4894 0.005222 0.000781
0.05 0.029 9.64175257
310.3448 0.003222 0.000482
0.02 0.013 10.8054124
692.3077 0.001444 0.000216
0.01 0.009 1000 0.001 0.00015 14.9613402

Group 5-6: NaOAc

16
y = -347.44x + 12.903
14
R2 = 0.832
molar conductance

12
10
Series1
8
Linear (Series1)
6
4
2
0
0 0.01 0.02 0.03 0.04
square root of c
- all data
 Group 5-6: NaOAc

12 y = -277.24x + 11.328
R2 = 0.9627
10
molar conductance

8
Series1
6
Linear (Series1)
4

0
0 0.01 0.02 0.03 0.04
square root of c
- removed outliers
Y-intercept = 11.328 = λ0, NaOAc
Group 5-6
M of NaCl Current Resistance (Ω) Conductance (Ω-1) Specific Molar
(A) Conductance Conductance
(Ω-1 cm-1) (Ω-1 cm2 mole-1)
1 0.178 2.95902062
50.5618 0.019778 0.002959
0.5 0.15 4.9871134
60 0.016667 0.002494
0.2 0.083 6.8988402
108.4337 0.009222 0.00138
0.1 0.047 7.81314433
191.4894 0.005222 0.000781
0.05 0.029 9.64175257
310.3448 0.003222 0.000482
0.02 0.013 10.8054124
692.3077 0.001444 0.000216
0.01 0.009 1000 0.001 0.00015 14.9613402

Group 5-6: NaCl

16
14 y = -347.44x + 12.903
R2 = 0.832
molar conductance

12
10
Series1
8
Linear (Series1)
6
4
2
0
0 0.01 0.02 0.03 0.04
square root of c
- all data
 Group 5-6: NaCl

12
y = -277.24x + 11.328
10 R2 = 0.9627
molar conductance

8
Series1
6
Linear (Series1)
4

0
0 0.01 0.02 0.03 0.04
square root of c
- removed outliers
Y-intercept = 11.328 = λ0, NaCl

From the graphs of [HCl vs. conductance and the square root of C vs. molar
conductance, it can be observed that molar conductance decreased as C increased and Ls is
almost directly proportional to C. Theoretically, the conductance must increase gradually until
the equivalence point is reached, then increase sharply afterwards.

D. Determination of Ionization Constant of a Weak Electrolyte by Conductance

Measurement
Sample Computation:
• α = λm/λo,HOAc
= λm /(λoNaOAc + λoHCl – λoNaCl)
= 0.00014213/ (11.328 + 0.0513 – 11.328) mho cm2 mol-1
= 2.770565302 x 10-3

• HOAc = H+ + OAc-

C-C α Cα Cα
2
Ka = (C α )/(1- α)
= (1(0.00277)2)/(1-0.00277)
= 7.69765 x 10-6

Group 5-6
M HoAc Current Resistance Conductance Specific Molar Degree of Ionization
-1
(A) (Ω) (Ω ) Conductance Conductance Ionization (α) constant
(Ω-1 cm-1) (Ω-1 cm2 mole-1) (Ka)

1 0.00855 0.00014213
1052.632 0.00095 0.000142 0.00277062 7.69765E-06
0.2 0.00490 0.00040728

1836.735 0.000544 8.15E-05 0.0079392 6.35353E-05

0.1 0.00380 0.0006317
2368.421 0.000422 6.32E-05 0.01231386 0.000153522
0.05 0.00248 0.00082454

3629.032 0.000276 4.12E-05 0.01607283 0.000262556

0.02 0.00171 0.00142133
5263.158 0.00019 2.84E-05 0.02770619 0.000789507
0.01 0.00135 0.0022442

6666.667 0.00015 2.24E-05 0.04374661 0.002001317

How does dilution affect the degree of ionization of acetic acid?

 Ka increases as dilution increases.

Theoretically, as the solution becomes more dilute, the degree of ionization must
decrease because water posses a common ion which suppresses the ionization and
promotes the formation instead of acetic acid.

E. Determination of the Solubility Product Constant by Conductance Measurement

Ca(OH)2  Ca2+ + 2OH-
I = 0.92 A
R, Ca(NO3)2= 9V / 0.92 A = 9.782608696 Ω
L = 1/R = 0.102222222 Ω-1
Ls,soln = K / R = 0.149613402 cm-1 / 9.782608696 Ω = 0.015293814 Ω-1 cm-1
Ls,solute = Ls,soln – Ls,solvent = 0.015293814 Ω-1 cm-1 - 0.58 x 10-7 = 0.015293756 Ω-1 cm-1
Λ, Ca = Ls, solute / C = 0.015293756 Ω-1 cm-1
0.1 mol x 1 Liter
L 1000 cm3
= 152.93756 Ω-1 cm2 mole-1
Λ0,Ca(OH)2 = lCa2+ + 2lOH-
= 2(59.50) + 2(198)
= 515 mho cm2 mole-1
Λ0 = 1000* Ls / C; C = 1000* Ls / Λ0
C = (0.015293756 Scm-1 / 515 Scm2mole-1) x (1000cm3/1L)
C = 0.029696613 M

Ksp, Ca(OH)2 = [C][2C]2 (theoretical = 6.5 x 10-6)

= 4 C3 = 4(0.029696613)3 = 1.045764507 x 10-4

Theoretical values (Equivalent Ionic Conductances at Infinite Dilution, 25°C):

Table -13-9. Maron, Samuel H. and Lando, Jerome B. Fundamentals of Physical Chemistry.
 Using conductance measurements, the solubility product constant of the difficultly
soluble Ca(OH)2 was determined. The Ls of the solute was determined first. It was equated
with the Ls of the solution because the solution is very dilute because Ca(OH)is very sparingly
soluble. The Ksp that we obtained was slightly off from the theoretical value which is of the
order 10-4. (theoretical = 6.5 x 10-6; experimental = 1.045764507 x 10-4).

F. Determination of Solubility Product Constant by Conductance Measurement

Plot VTitrant vs Conductance

Conductimetric Titration

0.06

0.05

0.04
conductance

0.03 Series1

0.02

0.01

0
0 10 20 30 40
volume of titrant (ml)

Vtitrant at equivalence point ≈ 14.5 ml

Concentration of unknown = 0.041428571 M
M1V1 = M2V2
(0.1 M NaOH)(0.0145L) = M2 (0.0145 L)
M2 (acid) = (0.10 moles/L NaOH x 14.5 ml x 1L/1000ml) / (35 ml x 1L /1000ml)
M = 0.041428571 M

For the conductimetric titration, the plot showed that the equivalence point was when
Vtitrant ≈ 14.5 ml (extrapolate manually), and the computed M acid = 0.041428571. We can also
deduce from the plot that the unknown analyte is a strong acid because of the V-shaped
graph, which is characteristic of strong electrolytes when titrated with a strong base.
Answers to Questions

1. How does molar conductance vary with concentration?

Based on the equation λm = 1000 Ls/ C, it can be inferred that as concentration of the
solution, C, increases, the molar conductance Λm, decreases.

As the concentration, C, decreases, molar conductance, Λm, increases for both strong
and weak electrolytes, while as C decreases, molar conductance increases.

In the determination of solubility product, Ls is dependent on C – as C increases for

strong electrolytes, Ls increases sharply. If C decreases, Ls decreases. However,
molar conductance still increases because the decrease in Ls is compensated by the
decrease in C.

2. Do the solutions obey Kohlrausch’s Law of independent migration of ions at infinite

dilution? Support and explain your answer.

Kohlrausch’s law of independent migration is applicable at infinitely dilute solutions

only. Based on the calculations, it can be deduced that the experimental solutions
used were concentrated since the solutions did not obey Kohlrausch’s law. If the
solution obeys Kohlrausch’s law, λ0 = λm. The two quantities obtained were not
equal, thus proving that the solutions did not obey the law.

3. How does dilution affect the degree of ionization of acetic acid?

According to Kohlrausch and Heydweiller, no matter how long and how carefully
purified, water will still exhibit a definite small conductance. Recall that the degree of
ionization is α = λm/ λ0. Since for strong and weak electrolytes, molar conductance λm
increases with decreasing concentration, diluting a solution of acetic acid (a weak
electrolyte) will increase λm. But then, water possesses a common ion with acetic
acid, H+ - hence the degree of ionization, α, will decrease.

References:

Atkins, Peter and de Paula, Julio. Atkins Physical Chemistry, 7th edition.
Laidler. Meisler. Physical Chemistry, 3rd edition
Maron, Samuel H. and Lando, Jerome B. Fundamentals of Physical Chemistry.
http://www.tau.ac.il/~phchlab/experiments/Conductivity/conductivity.htm
http://www.tpub.com/neets/book1/chapter1/1p.htm
http://www.corrosion-doctors.org/Electrochem/conductivity.htm