Section C – Analytical reactions in solution

C10 C ONDUCTIMETRY

Key Notes

Movement of ions

Ions in solution or in molten ionic solids will move when

an electric field is applied. The speed of movement
will depend on the size and charge of the ion. In
ionic solutions, the ions carry the current, but Ohm’s
law still applies. Increasing the number of ions
increases the conductance. Since analysts are
concerned with concentrations, it is preferable to
compare molar conductivities, which depend on the
chacteristics of the ions. If the number or nature of
ions present in a cell change, then the conductance
will change. This is useful for many types of
titration, including some in nonaqueous media.
Other topics in Section C.

Conductance
Conductivity

Conductimetric titrations

Related topics

Movement of ions

When an electric field is applied across a solution, a

force is exerted on the ions that will cause them to
move. Positive ions will move toward the more
negative electrode, negative ions toward the more
positive, but each will carry current. The speed with
which the ions move usually depends on: (i) (ii) (iii)
(iv) the electric field strength (V m-1); the charge z
on the ion; the size of the ion in solution; and the
viscosity of the solvent.

In water, the hydrogen ion, H3O+, and the hydroxyl ion,

OH-, are small, and move most rapidly by a very fast
exchange with the molecules of water. In dilute
solutions, the ions move independently of each
other. For an electric field of 1 V m-1, the ionic
speed is called the mobility, ui. Table 1 gives the
ionic size and mobility of selected ions in aqueous
solutions at 25∞C. It is worth noting that despite
their larger size in crystals, hydrated potassium ions
are smaller than hydrated sodium ions when in
solution and move faster.

Table 1. Ion Na K+ FClBr+

Selected vales of mobility and ionic radius 108 ui/m2 s-1
V-1 5.2 7.6 5.5 7.9 8.1 ri /nm 0.18 0.13 0.17 0.12
0.12
C10 – Conductimetry

105
Similar rules apply to anions. Also, potassium ions and
chloride ions have very similar mobilities. This is
useful when ‘salt bridges’ are needed (see Topic
C2). If ions are present in other solvents, such as
liquid ammonia, they will conduct in a similar way,
but their mobilities will be different. Conductance
Ohm’s law still applies to relate the current, I, to the
applied voltage, E, and the resistance, R, or to the
conductance, G = 1/R. I = E/R = EG G is related to
the concentration of ions and has units of ohms-1 or
siemens (W-1 or S). In order to measure the
conductance of a solution, a conductance cell is
used. It has two electrodes, often platinum, coated
with platinum black, separated by a fixed distance.
Connecting these to a conductance meter, or more
simply to a Wheatstone bridge, the conductance
may be measured directly. In order to prevent
electrolysis (see Topics C2, C9) taking place, which
would change the concentrations in the solution, the
bridge uses alternating current. Plastic and flow-
through conductance cells are also available In any
conductor, the conductance depends on the cell
dimensions and on the characteristics of the
conducting medium. For a cell with electrodes of
area A, set a distance l apart: G = k/(l/A) where k is
called the conductivity of the solution with units of
W-1 m-1 or S m-1. So that the results from different
cells and solutions may be compared, the cell
constant, K = (l/A) is measured using a solution of
known conductivity, often 0.1 M aqueous potassium
chloride, which has a conductivity k =1.288 W-1 m-1
at 25∞C. Conductivity Although it is often possible
to work directly with conductance, it is useful to
know the conductivity and molar conductivity when
results are to be compared. From the equations
above: k = G(l/A) Since the analyst is concerned with
molar concentrations, and the conductivity depends
 mostly on the amounts of ions present, the molar
conductivity Lm is defined by: Lm = k/c where Lm
has units of W m mol-1 provided that the
concentration c is expressed in mol m-3 (= 1000 M).

2 -1

Example When immersed in a 0.1 M aqueous solution of

KCl at 25∞C, a conductance cell had G = 8.59 ¥ 10-3
W-1. For 0.1 M HCl, using the same cell, the
conductance was measured as 2.57 ¥ 10-2 W-1.
Calculate the conductivity and molar conductivity of
the HCl. For the KCl calibration: k = G(l/A) = 8.59 ¥
10-3 ¥ (l/A) = 1.288 W-1m-1 Thus (l/A) = 149.9 m-1
and for HCl, k = 3.85 W-1 m-1

106

Section C – Analytical reactions in solution

Lm = k/c = 3.85/100 = 0.0385 W-1 m2 mol-1 For strong electrolytes, it must be

noted that, because of ionic interaction and the effects of the ionic atmosphere,
the molar conductivity decreases as the concentration increases, according to
the Onsager equation: Lm = Lom - K c where Lom is the molar conductivity at
infinite dilution, and K is a constant, dependent on temperature and the solute.
For weak electrolytes, the ionic concentration depends on the dissociation
constant, and since the relationship of the dissociation constant, K to the degree
of ionization a is, for a weak acid, approximately: K = ca2/(1 - a) The molar
conductivity of a weak electrolyte may be written: Lm = aLom These equations
show that, while Lm for a strong electrolyte decreases almost linearly with the
(c)1/2, for weak electrolyes such as ethanoic acid, it decreases approximately as
(1/c)1/2. More details will be found in textbooks of physical chemistry. Direct
measurement of concentration is possible. The presence of sodium chloride, or
other ionic species will increase conductance, and by knowing the molar
conductivity, the concentration may be found by measuring the conductivity of
C10 – Conductimetry

105
Similar rules apply to anions. Also, potassium ions and
chloride ions have very similar mobilities. This is
useful when ‘salt bridges’ are needed (see Topic
C2). If ions are present in other solvents, such as
liquid ammonia, they will conduct in a similar way,
but their mobilities will be different. Conductance
Ohm’s law still applies to relate the current, I, to the
applied voltage, E, and the resistance, R, or to the
conductance, G = 1/R. I = E/R = EG G is related to
the concentration of ions and has units of ohms-1 or
siemens (W-1 or S). In order to measure the
conductance of a solution, a conductance cell is
used. It has two electrodes, often platinum, coated
with platinum black, separated by a fixed distance.
Connecting these to a conductance meter, or more
simply to a Wheatstone bridge, the conductance
may be measured directly. In order to prevent
electrolysis (see Topics C2, C9) taking place, which
would change the concentrations in the solution, the
bridge uses alternating current. Plastic and flow-
through conductance cells are also available In any
conductor, the conductance depends on the cell
dimensions and on the characteristics of the
conducting medium. For a cell with electrodes of
area A, set a distance l apart: G = k/(l/A) where k is
called the conductivity of the solution with units of
W-1 m-1 or S m-1. So that the results from different
cells and solutions may be compared, the cell
constant, K = (l/A) is measured using a solution of
known conductivity, often 0.1 M aqueous potassium
chloride, which has a conductivity k =1.288 W-1 m-1
at 25∞C. Conductivity Although it is often possible
to work directly with conductance, it is useful to
know the conductivity and molar conductivity when
results are to be compared. From the equations
above: k = G(l/A) Since the analyst is concerned with
molar concentrations, and the conductivity depends
 mostly on the amounts of ions present, the molar
conductivity Lm is defined by: Lm = k/c where Lm
has units of W m mol-1 provided that the
concentration c is expressed in mol m-3 (= 1000 M).

2 -1

Example When immersed in a 0.1 M aqueous solution of

KCl at 25∞C, a conductance cell had G = 8.59 ¥ 10-3
W-1. For 0.1 M HCl, using the same cell, the
conductance was measured as 2.57 ¥ 10-2 W-1.
Calculate the conductivity and molar conductivity of
the HCl. For the KCl calibration: k = G(l/A) = 8.59 ¥
10-3 ¥ (l/A) = 1.288 W-1m-1 Thus (l/A) = 149.9 m-1
and for HCl, k = 3.85 W-1 m-1

106

Section C – Analytical reactions in solution

Lm = k/c = 3.85/100 = 0.0385 W-1 m2 mol-1 For strong electrolytes, it must be

noted that, because of ionic interaction and the effects of the ionic atmosphere,
the molar conductivity decreases as the concentration increases, according to
the Onsager equation: Lm = Lom - K c where Lom is the molar conductivity at
infinite dilution, and K is a constant, dependent on temperature and the solute.
For weak electrolytes, the ionic concentration depends on the dissociation
constant, and since the relationship of the dissociation constant, K to the degree
of ionization a is, for a weak acid, approximately: K = ca2/(1 - a) The molar
conductivity of a weak electrolyte may be written: Lm = aLom These equations
show that, while Lm for a strong electrolyte decreases almost linearly with the
(c)1/2, for weak electrolyes such as ethanoic acid, it decreases approximately as
(1/c)1/2. More details will be found in textbooks of physical chemistry. Direct
measurement of concentration is possible. The presence of sodium chloride, or
other ionic species will increase conductance, and by knowing the molar
conductivity, the concentration may be found by measuring the conductivity of
the solution. When very pure water is required for the
preparation of pure organics, or the manufacture of
semiconductor components, conductance
measurements are most useful. Provided dissolved
CO2 and other intrinsic factors are eliminated,
extremely pure water should have a conductivity of
around 150 mS m-1 (or 1.5 mS cm-1) at 25∞C. In
order to comply with regulations for some work, it
must be less than 200 mS m-1. Conductimetric
titrations Whenever titrations of ionic solutions are
carried out, the number and nature of the ions
change throughout the entire titration. If a strong
base, say NaOH, is titrated with a strong acid, HCl,
the reaction Na+ + OH- + H+ + Cl- = Na+ + Cl- +
H2O will first of all remove the OH- as
nonconducting water, so the conductance will
decrease until the end point. Then excess HCl will
increase the conductance. This gives a ‘V’ shaped
graph of conductance versus titer. If a mixture of
acids is used, they will be titrated in the order of
their strength. Figure 1(a) shows the conductimetric
titration of a mixture of HCl, boric acid and
ammonium chloride using NaOH. For precipitation
reactions: Ag+ + NO3- + Na+ + Cl- = AgCl(s) + Na+
+ NO3The sodium and silver ions have similar
conductivities, so adding NaCl solution does not
change the conductance much until the end point is
reached. Then the conductance rises with excess
NaCl. This is shown in Figure 1(b). The titrant is
often about ten-times more concentrated than the
sample solution, to avoid dilution errors.
C10 – Conductimetry

107

(a) 1.4 12 1000 x conductance

(b) 4 3.5 3 Conductance HCl 0 HB NH4Cl 0.5 1 1.5

Volume added (cm3) 2 2.5 2 1.5 1 0.5 0 0 1 3 4 2
Volume added (cm3) 5

1 0.8 0.6 0.4 0.2 0

Fig. 1. (a) Conductimetric titration of mixed acids with

1.0 M NaOH. (b) Conductimetric titration of 0.1 M
AgNO3 with 1.0 M KCl.

Conductimetric titrations may be carried out in

nonaqueous media. For example, phenols, which are
very weak acids in water, have enhanced acidity
when liquid ammonia is used as the solvent, and
may be titrated conductimetrically with an
ammoniacal solution of KOH.
Section D – Separation techniques

D1 S OLVENT

AND SOLID - PHASE EXTRACTION

Key Notes

Extraction techniques
Solvent and solid-phase extraction are two techniques
for separating mixtures of substances, either by
selective transfer between two immiscible liquid
phases or between a liquid and a solid phase.
Extraction efficiency is defined as the fraction or
percentage of a substance that can be extracted in
one or more steps. Selectivity is the degree to which
a substance can be separated from others in a
mixture. Procedures are based on the extraction of
nonpolar, uncharged species from an aqueous
solution into an immiscible organic solvent, or the
extraction of polar or ionized species into an
aqueous solution from an organic solvent. Sorbents
are particulate materials such as silica, chemically-
modified silica, alumina and organic resins that can
interact with and retain substances from solutions.
Retained substances can be subsequently released
back into a suitable solvent under controlled
conditions. Sample solutions are passed through the
sorbent under conditions where either the
analyte(s) are retained and matrix components
washed through or the reverse. Retained analytes
are removed with an alternative solvent before
completing the analysis. Solution equilibria (C1)

Extraction efficiency and selectivity

Solvent extraction

Solid-phase sorbents

Solid-phase extraction
Related topic