Experiment 4

Dependence of Saturation Activity of a Solute upon Temperature

Objective: to determine the enthalpy of solution of an organic acid by measuring the

saturation concentration at different temperature

Theory: the equilibrium between a solution and an insoluble part of the solute can be
described using chemical potential as

I ∅I I
μ B=μ B + RTln a B…..………………………………………………….. (4.1)

II ∅ II
μ B =μ B …………………………………………...……………………. (4.2)

With μ IB- chemical potential of the solute in the solution (phase I)

II
μ B - Chemical potential of the solid

∅I
μ B - Standard chemical potential of solute B in phase I

∅ II
μ B - Standard chemical potential of solute B in solid phase II

I
a B - Activity of solute B in the solution (phase I)

T and R – temperature and universal gas constant

The equilibrium condition for this system at constant temperature and pressure is

I II
μ B=μ B ……………………………………….………………………… (4.3)

Assuming equilibrium to be established, a small change of the chemical potential in one of

the two phase forces a similar change of chemical potential in the other phase. This is
expressed as follow:

I II
d μB =dμ B ………………………………………….………………….. (4. 4)
In general, the chemical potential depends on temperature, pressure and activity. Thus, the
total deferential of the chemical potential can be written as:

dμ= ( ∂∂ Tμ ) p, a
dT + ( ∂∂ μa ) p ,T
da+ ( ∂∂ μp ) T,a
dP…………………………. (4.5)

This leads to the following formulation of the chemical potential of the solute B in the
solution phase at constant pressure (differentiate equation 3.1):

I ∅I I I
dμ B=−S B dT + Rln a B dT + Rtdln a B ………………………...…… ..(4.6)

For the phase II (pure solid B)

II ∅ II
dμ B =−S B dT ……………………………………………………….... (4.7)

With S∅BI molar standard entropy of B in phase I, S∅BII molar standard entropy of B in phase
II

The molar entropy change of the phase transition of the solute B from the pure solid phase
II to the solution I is equal to the solution enthalpy (assuming constant pressure, ideal
behavior of the solution, and incompressibility of both phases).

∅ ∅I ∅ II
∆ S S =S B −S B …………………………………………………….. (4.8)

With ∆ S S ∅ standard entropy of solution

From the equations (3.6), (3.7) and (3.8) one can derive

( )
I ∅
dln a B ∆S S
− = ……………………………………………………... (4.9)
dT p RT

The entropy changes can be calculated from the corresponding enthalpy changes, because
the process of solution is assumed to be reversible at constant pressure.

( )
I ∅
dln aB ∆S H
= ……………………………………………………... .(4.10)
dT p R T 2
Where ∆ S H ∅ molar standard enthalpy of solution

After integration we obtain finally the following relation or the logarithm of the saturation
activity of the solute B.

∅
I −∆S H
ln a =
B +constant …………………………………….. ..(4.11)
RT

Materials and chemicals

 Water bath, electric stirrer thermometer (10-100 °C)

 pipette (10 mL) burette (50 mL)
 measuring cylinder(50 mL) Erlenmeyer flasks (about 250 mL)
 phenolphthalein solution sodium hydroxide solution (0.1 M or 0.5 M)
 sample of organic acid (given by the instructor).

Procedure

Heat the given solution of the acid to a temperature of about 30 °C. Allow the solubility
equilibrium to be established for at least 20 minutes. Stir the solution and heat on water
bath. Check that insoluble acid is still present in the flask. Pipette 10 mL of a saturated
solution without any solid out of the Erlenmeyer flask containing the sample. Add about 30
mL of distilled water to the 10 mL of saturated solution and titrate this with sodium
hydroxide using phenolphthalein as indicator. Note the temperature of the sample in the
water bath and the consumption of sodium hydroxide solution. Increase the temperature to
about 35 °C, 40°C, and 45 °C and repeat the procedure. Collect the data in a table as
shown below. The numbers of hydrogen ions per molecules of acid are given by the
instructor. Take this into account for the calculation of the molar concentration. Use the
molar concentration for computing the logarithm of concentration.

Table 4.1 Data gathering format

Temperatu Volume Concentration of the acid 1/T Log (c/

 re (T) of NaOH (c) K-1 mol L-1)
°C K in Ml N/equivl-1 M/mol L-1
… … …
… …

Calculation and Discussion

Calculate the saturation concentration of the organic acid for each temperature using the
data obtained by titration. Apply equation (3.11) replacing the saturation activity by the
saturation concentration in order to determine the enthalpy of solution. Thus, a straight line
dependence of the logarithm of saturation concentration on the reciprocal of temperature is
expected:

∅
I−∆ S H
log c =B + constant ………………………….………….. (4.12)
2.303 RT

The slope of the straight line of the best fit in a log versus 1/T diagram is therefore:
∅
−∆ S H
slope= ……………………………………………………….. (4.13)
2.303 R

Plot the graph using graph paper. Determine the enthalpy of solution from the slope of the
curve. Discuss your result.

Questions

1. What is the activity and activity coefficient for a given dilute solution?
2. What is in general, the equilibrium condition for a two-component-two-phase system?
3. What are the standard conditions for a) a solute, b) a solvent, c) a gas and d) a solid?
4. What statement concerning the solution enthalpy can be made when the solubility of a
solute is decreased at higher temperatures?
5. For some systems the curve logcB versus 1/T changes the slope at certain temperatures (e.g.
sulfanilic acid in water at 90 °C and 42 °C). What may be the reason for such a behavior?
 Experiment 9
Conductance of strong and weak electrolytes

Objectives: To study the relation between conductance and concentration for strong and
weak electrolytes, and to determine the solubility of sparingly soluble salt from
conductance data.

Theory: Solution of electrolytes conducts electric current by the transfer of ions. In order
to describe the conductivity of an electrolyte we consider a part of the electrolyte enclosed
within a conductivity cell of known dimensions. The conductivity, k of a conductor is
defined as the reciprocal of the resistivity, ρ.

1 l
k= = ……………………………………………………………….. (9.1)
ρ RA

k −conductivity , ρ−resistivity , R−resistanceofthepartoftheconductor ,

l−lengthoftheconductor , A−cross−sectionalareaofthecon ductor

The resistance of an electrolytic sample can be measured by the use of an electronic

instrument or by a Wheatstone bridge. In order to apply equation above to an electrolyte
solution a conductivity cell having a certain cell constant is used. Figure 9.1 shows the
construction of such a cell. Two electrodes are fixed at the walls of a glass tube, which can
be immersed in to the electrolyte sample. The cell constant can be determined by
measuring the resistance when the cell is placed in to an electrolyte of known specific
conductance. For the measurement of the electrolytic conductivity AC current with
frequency of about 1 KHz can be used. (Why is it impossible to use DC currents for the
measurement?). The electrodes of the conductivity cell are made of platinized platinum
having a high surface area in order to minimize electrode polarizations during the
measurements. The conductivity of an electrolyte solution is proportional to the number of
ions present per unit volume and in turn is influenced by the concentration as well as by
the extent to which the electrolyte is dissociated. From the measured conductivity we can
calculate the molar conductance or the equivalent conductance which is used to
characterize an electrolyte. They are defined as

k
Λ m= …………………………………………………………………. (9.2)
c

k
Λ ev = ………………………………………………………………… (9.3)
c ev

With Λ m−molar conductance , ionic conductivity ,

Λ ev −equivalentconductancec −molarconcentration , c ev −equivalentconcentration

For strong electrolytes Λ approaches a limiting value Λ ∞at infinite dilution. The following
empirical relationship has been suggested by Kohlrausch for the dependence of Λ on
concentration.

Λ= Λ∞ −b √ c ……………………………………………………………….(9.4)

With b constant, and this is known as Kohlrausch’s square root rule. Debye, Huckel and
Onsager derived a similar relation for strong electrolytes taking in to account the inter-
ionic interactions (electrostatic model). For dilute solutions the ions present in the
electrolyte can be assumed to move independently of each other. The value of Λ eq ,∞ of an
electrolyte can be expressed as

Λ eq ,∞ =∑ Λ eq ,i , ∞……………………………………………… (9.5)
i

Where Λ eq ,i , ∞−ionequivalentconductanceatinfinitedilution . It is called the rule of

independent ion migration (migration is defined as the particle movement caused by the
action of an electric field). The values of ion equivalent conductivities are compiled in
table 8.1.

For weak electrolyte (the degree of dissociation α is small in comparison to unity) the
equivalent conductivity Λ eqis given by:

Λ eq= Λ eq , ∞ . α ……………………………………………………..(9.6)

By measuring the equivalent conductivity of the weak electrolyte of a certain concentration

and by computing Λ eq ,∞ from the law of independent ion migration α can be determined.
This can be used to calculate the dissociation constant of the weak acid. The dissociation
proceeds according to the equation:

………………………………………………………………..(9.7)

Taking in to account that the degree of dissociation α gives the part of acetic acid (of total
concentrationc o ) which is decomposed, one will find

k =c ¿
H
+¿ c Ac−¿ ( α c o) (α c o)
= =c o
α
2
¿ ……………………………………………………(9.8)
c HAc (1−α )co 1−α

This relationship is called Ostwald’s dilution law. Conductivity measurement can be used
for the determination of the solubility of sparingly soluble salts. Salts of inorganic acids
and bases are mostly strong electrolytes. It can therefore be assumed that the dissolved part
of the salt is completely dissociated. For salts which show higher solubility this assumption
is not correct. When only a few parts of the salt is dissolved, however, then the solubility
can be determined from conductance data. Assuming that equation (9.3) is valid, the
equivalent concentration can be determined by measuring the specific conductance. The
value of Λ eqin equation (9.3) can be approximated using the corresponding value of Λ eq ,∞ .
The latter can be computed from the rule of independent ion migration. For the calculation
refer to table 9.1.

Table 9.1 Ion equivalent conductivities in aqueous solution at 25 °C

 Cation Λ eq ,i , ∞ (cm2equiv-1ohm-1) Anion Λ eq ,i , ∞ (cm2equiv-1ohm-1)

H+ 349.8 OH- 197.6

Li+ 38.7 F- 55.4

Na+ 50.1 Cl- 76.3

K+ 73.5 Br- 78.4

NH4+ 73.7 I- 76.9

Mg+2 53.1 SO42- 79.8

Ca+2 59.5 CO3- 72

Ba+2 63.7 CH3CO 40.9

O-

Pb+2 70 C2O42- 65

Remark: the unit “equiv” will be used in this manual strictly speaking this is no SI-unit.
The meaning of equiv is “mol equivalents” or “mol charges”. Despite this, the unit equiv is
widely used and its application prevents a misunderstanding between molar and equivalent
conductivities. The determination of electrolytic conductance is in general, based on the
measurement of resistance. It was mentioned before, that a Wheatstone bridge can be
applied for the measurement of resistance. Its circuit is shown in Figure 9.1. Irrespective of
the applied voltage from the power supply the instrument I indicate no current when the
values of the resistances follow the relation

R1 R3
= ……………………………………………………………(9.9)
R2 R4
If one the resistors is the conductivity cell and the other resistors are of known value and
adjusted in such a manner that the bridge current is zero, then the unknown resistance can
be calculated from equation (9.9). Mostly an AC power supply is used in the Wheatstone
bridge. Then, a headphone is applied as indicator, and the resistances are changed until the
noise is minimum. (Usually there is a signal of low intensity in the point of bridge
equilibrium too, why?).

a) b)

Figure 9.1 a)Conductivity cell b) Wheatstone bridge circuit

Sometimes, instead of a Wheatstone bridge a so-called conductivity meter is applied. This

is electronic ammeters, which allow the specific conductivity to be read directly taking in
to account the cell constant.

Materials

 Wheatstone bridge or conductivity meter conductivity cell

 Beaker (100 mL) pipettes (10, 25 mL)
 3 volumetric flasks (100 mL) 2 Erlenmeyer flasks (250 mL)
 Acetic acid (0.1 mol/L) unknown strong electrolyte (0.1 mol/L)
 Saturated solution of a sparingly soluble salt.

Procedure:
 The experiment consists of three parts.

1. Determination of Λ eq ,∞ of an unknown strong electrolyte. From the given stock solution

prepare a series of solutions of the following concentrations: 0.05, 0.025, 0.0125, 0.0063,
0.0032 and 0.0015 equiv/L. measure the conductance of the solutions and of distilled water
( K w ). Collect the data in a table as shown below:

Table 9.2

c ev K k −k w √ c ev Λ ev
Equiv/L 1 1
ohm-1m-1 ohm m -1 -1 ¿2 L2 cm2ohm-
1
equiv-1

0.1 … … … …
. . . . .
. . . . .
. . . . .

2. Determination of the dissociation constant of CH 3COOH. Repeat the procedure given

above starting from 0.1 molar acetic acid. Collect the data in a table as follows. Calculate α
in the table value Λ eq ,∞ which can be computed from table 9.1.

Table 9.3

c ev K k −k w Λ ev Λev 1 −1 α
2
α= ≡L
Λev , ∞ c ev 1−α
Equi ohm-1m-1 ohm-1m-1 cm2ohm- ----
-----
1
v/L equiv-1
0. … … … … … …
1 . . . . . .
. . . . . . .
. . . . . . .
.

3. Determination of the solubility of a salt. Determine the conductance of the solution of the
salt given by the instructor (use the clear filtrates of the saturated solution). Determine also
the conductance of distilled water. Repeat the measurements 5 times and collect the data
as:

Table 9.4

Number of k k −k w
measurement ohm-1m-1
-1 -1
ohm m

1 … …
. . .
. . .
. . .

Calculation and discussion

1. Calculate all values of table 8.2. For the determination of Λ ev ,∞ a graphical method should
be used. Plotting the data in a Λ ev versus√ c ev diagram a linear relationship will be expected
according to equation (8.3). Λ ev ,∞can be found from the ordinate intercept of the straight
line which fits the points best.
2. According to equation (8.8) the dissociation constant of acetic acid can be found from the
α
2
1
slope of the plot of the data in versus diagram:
1−α c ev
 2
α 1
=k (8.10)
1−α c ev
3. Using equation (8.2) calculate the equivalent concentration of the saturated solution of the
salt. For the calculation you should use Λ− Λw instead of Λ .

Questions

1. Why does water itself show certain conductivity?

2. Inform yourself about the classification of electrolytes and state examples for each group.
3. Will electrolytic solutions obey Ohm’s law? Give a reason for your answer.
4. Derive the condition (8.8) for the equilibrium bridge.