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Electrolytes
Objective
Introduction
Pure water does not conduct electricity, but any solvated ionic species would
contribute to conduction of electricity. An ionically conducting solution is called an
electrolyte solution and the compound, which produces the ions as it dissolves, is
called an electrolyte. A strong electrolyte is a compound that will completely
dissociate into ions in water. Correspondingly, a weak electrolyte dissolves only
partially. The conductivity of an electrolyte solution depends on concentration of the
ionic species and behaves differently for strong and weak electrolytes.
The conductance (L) is generally used for dealing with electrolytes and it is defined as
the reciprocal of the resistance of the solution
L (Ω-1) = 1
R Equation 1:
Once R is known, the conductivity or specific conductance (X) may be obtained from
X (Ω-1 cm-1) = _d
AR Equation 2:
where A and d are the area and separation between the electrodes of the cell.
and therefore
Equation 4: X=kL
For weak electrolytes, the increase of molar conductivity with increasing dilution is
ascribed to increased dissociation of the electrolyte molecules to free ions. The degree
of dissociation (α) at a given concentration C is given by
α= Λ
Λ0 Equation 6:
For strong electrolytes, the molar conductivity is higher than those of weak
electrolytes at high concentrations. As the electrolytes become dilute, the molar
conductivities also increase but is less steep than for weak electrolytes. For strong
electrolytes in dilute solution, the variation of molar conductivity with dilution can be
expressed as
For weak electrolytes, the values of Λ0 can be deduced from the limiting molar
conductivities of strong electrolytes using Kohlrausch’s law. Alternatively, Λ0 and the
dissociation constant of a weak electrolyte may be obtained from the Ostwald dilution
law
1 = _1 + CΛ
Λ Λ0 kaΛ02 Equation 8:
Apparatus
Conductivity meter, dilution flasks (100mL), pipette, burette and measuring cylinder.
Materials
Experimental Procedures
The specific conductance (X) of this solution is 2.768 x 10-3 Ω-1 cm-1.
2. Measurement of conductance
The procedure was repeated with hydrochloric acid, sodium chloride and
sodium acetate.
The conductance of water used was measured.
Resistance, R (Ω)
-3
C (mol dm ) CH3COOH HCl NaCl CH3COONa
0.1000 2883 31.91 96.04 166
0.0500 3669 63.79 193.3 297.9
0.0250 6440 122.70 366.0 600.5
0.0125 8605 243 717.1 1178
0.00625 12395 472.44 1438 2577
0.00312 18280 940.88 2825 4485
0.00156 25100 1823.4 5451 8975
0.00078 44970 3569.8 10400 17210
Conductance, L (Ω-1)
-3
C (mol dm ) CH3COOH HCl NaCl CH3COONa
-4
0.1000 3.469 x 10 0.0313 0.0104 6.024 x 10-3
0.0500 2.726 x 10-4 0.0157 5.173 x 10-3 3.357 x 10-3
-4
0.0250 1.553 x 10 8.150 x 10-3 2.732 x 10-3 1.665 x 10-3
-4
0.0125 1.162 x 10 4.115 x 10-3 1.395 x 10-3 8.489 x 10-4
0.00625 8.068 x 10-5 2.117 x 10-3 6.954 x 10-4 4.207 x 10-4
0.00312 5.470 x 10-5 1.063 x 10-3 3.540 x 10-4 2.230 x 10-4
-5
0.00156 3.984 x 10 5.484 x 10-4 1.835 x 10-4 1.114 x 10-4
0.00078 2.224 x 10-5 2.801 x 10-4 9.615 x 10-5 5.811 x 10-5
From Figure 1,
Λ0 (HCl) = 53.0 Ω-1 cm2 mol-1
At 0.05000 M, Λ = 0.7484, α = Λ / Λ0
= 0.7484 / 40.0
= 0.0187
At 0.01250 M, Λ = 1.2768, α = Λ / Λ0
= 1.2768 / 40.0
= 0.0319
At 0.00156 M, Λ = 3.5064, α = Λ / Λ0
= 3.5064 / 40.0
= 0.0877
ka = α2C
1-α
= (0.0187)2 (0.05 mol dm-3)
1 – 0.0187
= 1.782 x 10-5 M
Gradient of graph,
__1 = _(2.14 – 0.30) Ω cm-2 mol _
2
kaΛ 0 (4.75 – 0.60) x 10-5 Ω-1 cm-1
= 44337.35 mol cm-3
= 4.4337 x 107 mol dm-3
kaΛ 0 = 1 / (4.4337 x 107 mol dm-3)
2
The intercept at CΛ = 0,
1 = 0.04Ω cm-2 mol
Λ0
Λ0 = 1 / (0.04 Ω cm-2 mol)
Equilibrium constant,
ka = kaΛ20 /Λ20
= 2.2554 x 10-8 mol-1 dm3 / (0.25 Ω-1 dm2 mol-1)2
= 3.609 x 10-7 Ω2 mol dm-1
According to Atkins’ Physical Chemistry (8th edition) page 1007 Table 7.4, the
theoretical value of dissociation constant of acetic acid (ka) is 1.4 x 10-5 M.
From calculation, the experimental value of ka is 1.782 x 10-5 M.
According to lab manual Component A page 19, the theoretical value of molar
conductivity in the limit of zero concentration of acetic acid,
Λ0 = Λ+ + Λ-
= 34.96 + 4.09
= 39.05 mS m2 mol-1
Discussion
The solution conducts electricity through motion of the ions under the effect of an
electric field. At high concentrations, each ion is surrounded by other ions, both
positive and negative. The field affecting any particular ion changes slightly because
of these surrounding ions. At infinite dilution, the distance between nearest neighbor
ions is large, and only the effect of the applied electric field is felt by individual ions.
This is the reason for extrapolating the data to infinite dilution.
The conductivity of any particular ion will also be affected by the ease with which the
ion can more through the water. Hence different ions should contribute differently to
the total measured conductivity. The ease with which any ion moves through the
solution depends on considerations such as the total charge and the size of the ion;
large ions offer greater resistance to motion through the water than small ions.
Conclusion
The conductance (L) of potassium chloride, hydrochloric acid, sodium chloride and
sodium acetate range from 9.615 x 10-5 Ω-1 to 0.0104 Ω-1.
The experimental value of dissociation constant of acetic acid (ka) is 1.782 x 10-5 M.
The experimental value of molar conductivity of acetic acid (Λ0) is 40.0 Ω-1 cm2 mol-1
Precaution
2. Blot the inside of the electrode cell dry before the next measurement to avoid
water droplets diluting or contaminating the sample to be tested.
3. Before taking readings, always shake the electrode briefly to release possible air
bubbles trapped in the electrode.
4. Ensure that the electrode surfaces in the elongated cell are completely submerged
in the liquid.
5. Always stir to ensure that the solution is homogenous during the measurement.
References
1. http://www.csun.edu/~jeloranta/CHEM355L/experiment4.pdf
2. http://www-ec.njit.edu/~grow/conductivity.htm
3. http://wwwchem.uwimona.edu.jm:1104/lab_manuals/c10expt19.html
4. Atkins’ Physical Chemistry , Peter Atkins and Julio de Paula, (8th edition), Oxford
New York