CHEM 347

PHYSICAL CHEMISTRY LABORATORY

Experiment 4: Conductance of Electrolytes

Yaren Karakoç
Student ID Number: 2019206204
Partners: Barış Kamilçelebi
Section 2, Group 2

Experiment Date: 28.11.2024

Submission Date: 05.12.2024
Introduction
Conductance is a measure of ease of which a material allows electric current to go by (Belessiotis et al.,
2016). In solution of electrolytes, anions migrate to anode and cations to cathode which facilitate electrical
conductance (Tiwari et al., 2013). A strong electrolyte dissociates strongly in solution -and the solution of
strong electrolytes conduct electricity well via ion movement- whereas a weak electrolyte dissociates
poorly, and a non-electrolyte is not dissociated (Duncan, 1938). Resistance is a measure of the opposing
force to electric current (Khalifeh, 2020). Resistance is observed Ohm’s law (Moosbrugger, 2020):
V = I.R (1)
where V is voltage in volts (V), I is electric current in amperes (A) and R is resistance in ohms, Ω.
Resistance can be depicted by the following equation (Moosbrugger, 2020):
l
R= ρ (2)
A
l
where is the cell constant in which l is the length (m) and A is the area of cross-section (m2) of the
A
conductor while ρ is the specific resistance or resistivity in Ωm which is specific to conductor. Resistance
and conductance relate to each other in that conductance is the reciprocal of resistance with the unit Ω-1 or
S for siemens (Khalifeh, 2020). Similarly, specific conductance or conductivity of a material is the
reciprocal of its resistivity, represented by κ (Kappa) with the unit Sm-1 which equals to l/RA when
Equation 2 is rearranged (Sophocleous, 2017). Since l/A represents cell constant (Sophocleous, 2017):
cell constant = κ*R (3)
In a solution, conductivity is guided by concentration of solute ions which gives rise to the term “molar
conductivity” (Laidler et al., 2003) by the equation:
Λ = κ/c (4)
In Equation 4, Λ is the molar conductivity with Sm2mol-1 as units, κ is conductivity with the unit Sm-1,
and c, concentration can be written in mol per meter cubic.
As mentioned, strong electrolytes are good conductors due to complete solute dissociation and their high
molar conductivity is affected little by dilution (Hanibah et al., 2014). Strong electrolytes obey the
Kohlrausch’s law (Laidler et al., 2003):
Λ = Λ0 -Kc1/2 (5)
In Equation 5, Λ is the molar conductivity of the strong electrolyte, Λ0 is molar conductivity at infinite
dilution (no interaction between ions or zero solute concentration) or limiting molar conductivity, K is an
experimental value and c is concentration. Λ0 can be mathematically approximated by extrapolation of Λ
versus c1/2 graph at c1/2 = 0 (Hanibah et al., 2014). The limiting molar conductivity of strong electrolytes
can be broken down to independent contribution of negative and positive ions (Atkins et al., 2006):
Λ0 = ν+λ+ + ν-λ- (6)
where ν values represent the proportion of cations and anions after dissociation (for example for NaCl, ν+
and ν- are both 1 but for MgCl2 ν+ is 1 and ν- is 2) and λ values are the limiting molar conductivities of
each species.
Strong electrolytes show slow linear increase in Λ via dilution, but weak electrolytes’ molar conductivity
is exponentially related to concentration (Hanibah et al., 2014). Since weak electrolytes don’t ionize
completely, α, degree of ionization is an important parameter in calculation of limiting molar conductivity
in that (Hanibah et al., 2014):
Λ
Λ0
=α (7)

A weak electrolyte can be exemplified by a weak acid with the dissociation equilibrium (Atkins et al.,
2006):
HA ⇋ H+ + A- (8)
In Equation 8, the HA acid is in equilibrium with the dissociated species H+ and A-. If molar concentration
of the weak acid HA is c and α is the degree of ionization, the acid dissociation constant Ka is given by:
α2 c
Ka = (9)
(1−α)

The aim of this experiment is to find the limiting molar conductivity and acid dissociation constant of
acetic acid (HAc) which is a weak acid via measuring molar conductivities of HAc, HCl, KAc, KCl at
varying concentrations. This is done by calculating limiting molar conductivities of HCl, KAc, KCl which
are strong electrolytes via graphs acquired based on Equation 5 and finding degree of ionization of acetic
acid at different molar concentrations via Equation 7.

Methods
Glassware and Equipment

• 100mL Volumetric Flask ±0.10mL • Distilled Water

• 25mL Glass Pipette ±0.1mL • 0.02M KCl Solution
• Beakers • 0.02M HCl Solution
• Volumetric Flask Stoppers • 0.02M KAc Solution
• Pasteur Pipettes • 0.05M HAc (Acetic Acid) Solution
• Conductometer

Procedure
1. The cell constant “x” was noted as 0.482 cm-1.
2. In a beaker, distilled water filled. The conductometer was calibrated by measuring the conductivity of
distilled water via placing the conductivity cell inside the water.
3. Serial dilutions of 0.02M KCl solution were prepared. This was done by aliquoting 25mL of 0.02M
KCl solution by glass pipette into a 100mL volumetric flask. Then, the flask was filled up to 100mL
with 75mL distilled water. The flask was secured with a stopper and inverted several times for
complete mixing. 1/4 dilution was prepared in this way.
4. 1/16 dilution was prepared in a similar manner as in Step 3. 25mL of 1/4 dilution was transferred into
a new 100mL volumetric flask by pouring the solution into a beaker and pipetting from the beaker.
The volume was topped with distilled water to 100mL, and flask was inverted for mixing.
5. 1/64 dilution was prepared from 1/16 dilution like in Step 3.
6. 100mL 1/4, 1/16, 1/64 dilutions of HCl solution were prepared from the stock 0.02M HCl solution as
in Step 3 and 4.
7. 100mL 1/4, 1/16, 1/64 dilutions of KAc solution were prepared from the stock 0.02M KAc solution
as in Step 3 and 4.
8. 100mL 1/4, 1/16, 1/64 dilutions of HAc solution were prepared from the stock 0.05M HAc solution
as in Step 3 and 4.
9. The conductivity cell was rinsed with 1/64 dilution of KCl solution. Then, the solution was poured
into a beaker. The conductivity cell was immersed in 1/64 KCl solution and reading was noted.
10. Step 9 was repeated with 1/16 dilution of KCl solution and conductivity reading was noted.
11. Respectively, Step 9 was repeated with 1/4 dilution of KCl solution and undiluted KCl solution.
12. Steps 9-11 were repeated with HCl, KAc and HAc solutions. Conductivity readings were noted.

Results
In the experiment, the cell constant (x) was 0.482 cm-1. The conductivity of distilled water was measured
as 1.2 µScm-1 with the conductometer. Also, conductivities of HAc, HCl, KAc, KCl solutions of different
concentrations were measured with the conductometer. For each solution, 1/4, 1/16 and 1/64 dilutions
were prepared from stock solutions and stock solutions were given as dilution 1. Conductivities were
measured at these 4 concentrations for HAc, HCl, KAc, KCl and given in Table 1.

Table 1. Conductivities of KCl, HCl, KAc and HAc solutions at different dilutions.

Solution Dilution Measured Conductivity* / µScm-1

1 4520
1/4 1210.
KCl
1/16 314
1/64 83.3
1 5750
1/4 1521
HCl
1/16 432
1/64 113.4
1 1648
1/4 447
KAc
1/16 118.5
1/64 33.2
1 228
1/4 100.0
HAc
1/16 48.8
1/64 24.3
* Due to the varying units of the conductometer for different measurements, the conductivity values do
not have the same decimal places. The conductivity measurements were displayed in µScm-1 and mScm-1
by conductometer and all measurements were converted to µScm-1 units for convenience.
Calculations
Firstly, the dilutions were converted to molarities for further calculations. The conversion was done by
multiplying the starting concentration in molarity by dilution factor. The converted values are presented in
Table 2. In Table 2, dilution 1 refers to undiluted starting solutions given in Methods section. For example
if starting concentration is 0.02M, 1/16 dilution is:
0.02M * 1/16 = 0.00125M = 0.00125 molL-1

Table 2. Corresponding concentrations in molarity (molL-1) for different dilutions of KCl, HCl, KAc, HAc
solutions.

Solution Dilution Concentration / molL-1 Solution Dilution Concentration / molL-1

1 0.02 1 0.02
1/4 0.005 1/4 0.005
KCl KAc
1/16 0.00125 1/16 0.00125
1/64 0.0003125 1/64 0.0003125
1 0.02 1 0.05
1/4 0.005 1/4 0.0125
HCl HAc
1/16 0.00125 1/16 0.003125
1/64 0.0003125 1/64 0.00078125

The measured conductivities in Table 1 were converted to corrected conductivities by subtracting the
conductivity of distilled water from each value. Then, molar conductivity of each solution in Table 1 (all
dilutions including undiluted stock solutions) was calculated by dividing the corrected conductivity by
concentration. The unit of molar conductivity was adjusted to Sm2mol-1. For molar conductivity versus
square root of concentration graphs, the concentration values were converted to mol/m3 units, and their
square root was taken. Finally, from the cell constant value (x = 0.482 cm-1), resistance values for all
solutions were calculated. The entirety of these calculations, with detailed explanation of implemented
equations is presented below for 1/16 dilution of KCl solution as an example:
Conductivity of distilled water: 1.2 µScm-1
Measured conductivity of 1/16 dilution of KCl solution (Table 1): 314 µScm-1
Corrected conductivity = measured conductivity – conductivity of distilled water = 314 – 1.2 = 312.8
µScm-1
κ = Corrected conductivity of 1/16 dilution of KCl solution = 312.8 µScm-1 ≈ 313 µScm-1

Λ = Molar conductivity of 1/16 dilution of KCl solution = κ/c from Equation 4.

Λ = 312.8 µScm-1 / 0.00125 molL-1
Units conversions for conductivity and concentration is done to acquire molar conductivity in Sm2mol-1:
312.8 µScm-1 = 312.8 * 10-6 * S/µS 1/10-2 * cm/m-1 * = 0.03128 Sm-1
0.00125 molL-1 = 0.00125 moldm-3 = 0.00125 * 1/(10-1)3 * dm3/m-3 = 1.25 molm-3
Λ = 0.03128 Sm-1 / 1.25 molm-3 = 0.025024 Sm2mol-1 ≈ 0.0250 Sm2mol-1

√concentration = √1.25 molm−3 = 1.118033989 mol1/2m-3/2 ≈ 1.12 mol1/2m-3/2

Resistance is found from Equation 3:

cell constant = x = 0.482 cm-1 = κ*R
Resistance = R = 0.482 cm-1 / κ
κ = 312.8 µScm-1 = 312.8 * 10-6 * S/µS = 3.128 * 10-4 Scm-1
R = 0.482 cm-1 / 3.128 * 10-4 Scm-1 = 1540.920716 S-1 = 1540.920716 Ω ≈ 1540 Ω

Table 3. Concentration, corrected conductivity, molar conductivity, square root of concentration and
resistance values for every dilution of KCl, HCl, KAc, HAc solutions.
Molar
Concentration Corrected Conductivity* Concentration1/2 ** Resistance*
Solution Conductivity*
/ molL-1 / µScm-1 / mol1/2m-3/2 /Ω
/ Sm2mol-1
0.02 4520 0.0226 4.472135955 107
0.005 1209 0.02418 2.236067977 398.7
KCl
0.00125 313 0.0250 1.118033989 1540
0.0003125 82.1 0.0263 0.559016994 5870
0.02 5750 0.0287 4.472135955 83.8
0.005 1520. 0.03040 2.236067977 317.1
HCl
0.00125 431 0.0345 1.118033989 112
0.0003125 112.2 0.03590 0.559016994 4296
0.02 1647 0.008234 4.472135955 292.7
0.005 446 0.00892 2.236067977 1080
KAc
0.00125 117.3 0.009384 1.118033989 4109
0.0003125 32.0 0.0102 0.559016994 15100
0.05 227 0.000454 7.071067812 2120
0.0125 98.8 0.000790 3.535533906 488
HAc
0.003125 47.6 0.00152 1.767766953 10100
0.00078125 23.1 0.00296 0.883883476 20900
* These values are rounded off to the closest significant figure in their calculations. In further
calculations, actual values are used. For exact values, please see the supplementary Excel file.
** The square root of concentration was given with exact values without rounding because concentration
values were not measured, and they were taken as exact numbers.
For Kcl, HCl and KAc solutions, molar conductivity (Λ) versus concentration1/2 graphs were drawn
utilizing values in Table 3. These graphs are given in Figures 1 to 3, respectively.

Molar Conductivity of KCl Solutions

0.027
Molar Conductivity / Sm2mol-1

0.026
y = -0.0009x + 0.0263
0.025 R² = 0.9494

0.024

0.023

0.022
0 1 2 3 4 5
Concentration1/2 / mol1/2m-3/2

Figure 1. Molar conductivity (Λ) of KCl solutions plotted against square root of concentration. The
trendline has the equation: “y = -0.0009x + 0.0263” and R² value of 0.9494.

Molar Conductivity of HCl Solutions

0.037
Molar Conductivity / Sm2mol-1

0.035
y = -0.0018x + 0.0362
0.033 R² = 0.8796
0.031
0.029
0.027
0.025
0 1 2 3 4 5
Concentration1/2 / mol1/2m-3/2

Figure 2. Molar conductivity (Λ) of HCl solutions plotted against square root of concentration. The
trendline has the equation: “y = -0.0018x + 0.0362” and R² value of 0.8796.
 Molar Conductivity of KAc Solutions
0.0105
Molar Conductivity / Sm2mol-1

0.01

0.0095
y = -0.0005x + 0.0102
0.009 R² = 0.8846

0.0085

0.008
0 1 2 3 4 5
Concentration1/2 / mol1/2m-3/2

Figure 3. Molar conductivity (Λ) of KAc solutions plotted against square root of concentration. The
trendline has the equation: “y = -0.0005x + 0.0102” and R² value of 0.8846.

From Figures 1 to 3, the limiting molar conductivities (Λ0) of KCl, HCl, KAc solutions were obtained
from extrapolating the graph to zero concentration. These values are y-intercepts of trendlines’ equations
in each figure, and they are given in Table 4. Λ0 (HAc) was calculated from the following equation:
Λ0 (HAc) = Λ0 (HCl) + Λ0 (KAc) - Λ0 (KCl) (10)
Equation 10 can be validated by writing limiting molar conductivities in right side with independent ions
as in Equation 6 and taking all ν values as 1:
Λ0 (HAc) = λH+ + λCl- + λK+ + λAc- - (λK+ + λCl-) = λH+ + λCl- + λK+ + λAc- - λK+ - λCl- = λH+ + λAc- (11)
From Equation 10, limiting molar conductivity of acetic acid:
Limiting molar conductivity of acetic acid = Λ0 (HAc) = 0.0362 + 0.0102 - 0.0263 = 0.0201

Table 4. Limiting molar conductivities of solutions.

Solutions Limiting Molar Conductivity / Sm2mol-1
KCl 0.0263
HCl 0.0362
KAc 0.0102
HAc 0.0201

From Equation 7, degree of ionization (α) of acetic acid solutions were calculated by dividing molar
conductivities in Table 3 at 4 concentrations to limiting molar conductivity of 0.0201 Sm2mol-1 in Table 4.
Then, acid dissociation constant for acetic acid (Ka) is calculated via Equation 9. Finally, the square root
of multiplication of α and molar concentration was found for each concentration to graph acid dissociation
constant for acetic acid versus this value (Figure 4). As an example, for 1/16 dilution, 0.003125 molL-1 of
HAc:
α = Λ / Λ0 = 0.0015232 Sm2mol-1 / 0.0201 Sm2mol-1 = 0.075781095 ≈ 0.0758
α2 c 0.1471044782 0.003125
Ka = = = 1.94177 * 10-5 molL-1 ≈ 1.94 * 10-5 molL-1
(1−α) 1−0.147104478

√αc = √0.075781095 ∗ 0.003125 = 0.015388825 mol1/2L-1/2 ≈ 0.0154 mol1/2L-1/2

Table 5. Degree of ionization (α), acid dissociation constant (Ka) and (αc)1/2 values for different acetic
acid concentrations.

Degree of
Concentration of HAc Solutions / molL-1 Ka for HAc* / 10-5 molL-1 (αc)1/2 * / mol1/2L-1/2
Ionization*
0.05 0.0226 2.60 0.0336
0.0125 0.0393 2.01 0.0222
0.003125 0.0758 1.94 0.0154
0.00078125 0.147 1.98 0.0107
* These values are rounded off to the closest significant figure in their calculations. In further calculations
and graph constructions, actual values are used. For exact values, please see the supplementary Excel file.

Acid Dissociation Constant of HAc versus (αc)1/2

0.000027
y = 2.85E-04x + 1.55E-05
0.000025
R² = 8.09E-01
0.000023
Ka / molL-1

0.000021

0.000019

0.000017

0.000015
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04
(αc)1/2 / mol1/2L-1/2

Figure 4. The acid dissociation constant of acetic acid found at 4 different concentrations plotted against
square root of multiplication of α and molar concentration. The graph yields a trend line with the equation:
“2.85 * 10-4x + 1.55 * 10-5” and R² of 0.809.
Average of Ka for acetic acid is found by adding Ka values in Table 5 and diving them by 4:
Average Ka = [(2.60518 * 10-5) + (2.01203 * 10-5) + (1.94177 * 10-5) + (1.98219 * 10-5)] / 4 = 2.13529 *
10-5 molL-1 ≈ 2.135 * 10-5 molL-1
Also, a second Ka value is found from the extrapolation of the graph in Figure 4 to zero concentration
which the y-intercept of the trend line equation in Figure 4. Then, these values are compared with the
literature value of 1.75 * 10-5 molL-1 (J. Am. Chem. Soc., 2004) and each other to calculate percent errors.
Percent error = |experimental value - expected value| / expected value * 100
Percent error in average Ka = |2.135 * 10-5 molL-1 - 1.75 * 10-5 molL-1| / 1.75 * 10-5 molL-1 * 100 =
22.016652 ≈ 22 %
Extrapolated Ka = y-intercept of Figure 1 = 1.55 * 10-5 molL-1
Percent error in extrapolated Ka = |1.55 * 10-5 molL-1 - 1.75 * 10-5 molL-1| / 1.75 * 10-5 molL-1 * 100 =
11.428571 ≈ 11 %
Percent error in extrapolated Ka compared to average Ka = = |1.55 * 10-5 molL-1 - 2.135 * 10-5 molL-1| /
2.135 * 10-5 molL-1 * 100 = 27.410376 ≈ 27 %

Discussion
In this experiment, the objective was to determine the limiting molar conductivity and acid dissociation
constant for acetic acid. Acetic acid being a weak acid (and a weak electrolyte) with low dissociation, this
was done by utilizing strong electrolytes. To obtain these values, firstly, conductivity of different
concentrations of KCl, HCl, KAc and HAc solutions were measured. From Table 3, the lowest molar
conductivity values were that of acetic acid (HAc) which is expected since it is a weak electrolyte with
low conductivity. When other 3 solutions which were strong electrolytes were compared, for the same
concentrations, the strength of molar conductivity follows this order: HCl solutions, KCl solutions and
KAc solutions. The same order is also observed in limiting molar conductivities (Table 4). HCl having the
highest limiting molar conductivity might be related to H+ species having an extremely high limiting ion
concentration of 349.82 Scm2mol-1 compared to other ions: Cl-: 76.34, K+:73.52 and Acetate-:40.9
Scm2mol-1 (Duncan, A., 1938). When compounds are paired with the ions they constitute of, it is plausible
to find this relation. Resistance values on the other hand, are inversely proportional to molar conductivity
values (Table 3). It is also observed that acetic acid has the highest resistance values. This is also
anticipated since it is the only weak electrolyte in the experiment. For all 4 compounds, resistance values
increase upon dilution. This can be explained by an increase in resistivity which is the inverse of
conductivity. In Table 3, it is observed that conductivity decreases when solutions are diluted. Therefore,
lower concentration causes lower conductivity which causes higher resistance due to inverse relation
between conductivity and resistivity.
For all 4 substances, conductivity decreases via dilution, but molar conductivity increases via dilution
(Table 3). The 3 strong electrolytes produced a linear molar conductivity versus concentration1/2 graph
with negative slopes (Figures 1 to 3) as expected due to Equation 5. This linear relation is established by
moderate to high R2 values (Lewis-Beck et al., 1990) of 0.9494, 0.8796 and 0.8846 for KCl, HCl and KAc
respectively. High R2 values suggest that the data is not spread around the trend line and approximation
should be successful. The graph of acetic acid was not presented here because it doesn’t follow a linear
trend (Hanibah et al., 2014) but if it is drawn (provided in supplementary Excel file), it can be observed
that data is in line with expected trend, and the graph follows an exponential path supported by literature.
The limiting molar conductivity of acetic acid was calculated from limiting molar conductivities of strong
electrolytes. Therefore, it is crucial to obtain correct values because degree of ionization and acid
dissociation constant calculations are based on limiting molar conductivity of acetic acid. Only four
concentrations were used in data taking. If more concentrations are added to the experiment, the graphs
obtained, therefore the limiting molar conductivities obtained would be more reliable. If the experiment is
repeated, adding two or three more concentrations can increase the accuracy and precision of Λ0 obtained.
According to Table 5, degree of ionization values increases with dilution. This is expected as it is found
via dividing molar conductivity by Λ0. As molar conductivity increases strongly upon dilution in weak
electrolytes (Hanibah et al., 2014), degree of ionization follows the same trend. The four Ka values
calculated from degree of ionization and molar concentration are very close to each other (Table 5) and
data does not show an obvious outlier. Further statistical tests should be done to support this primary
observation. The graph of Ka versus (αc)1/2 (Figure 4) follows a linear trend with and R2 of 0.809. This
value is moderate and experimental errors discussed more in detail in Sources of Errors sub-section can
provide more insight into causes. When Ka values averaged from Table 5 and Ka value found from y-
intercept of Figure 4 are compared to theoretical value and with each other, percent errors lower than 30%
are found. Considering the sensitivity of the equipment used and limited data points, this low error rate
suggests that experiment was successful in estimating the acid dissociation constant and Λ0 for acetic acid.

Sources of Error
In this experiment, conductometer was used to measure conductivities. This is the only data implemented
in the experiment, therefore errors caused by the instrument are crucial. Heat fluctuations can cause
random error. But conductivities can change with temperature. Therefore, temperature changes are
systematic error sources in this experiment. Since work is done with an electrical device noise due to
electrical, pressure, heat fluctuations can also cause systematic and random errors. A non-calibrated device
can cause systematic errors. Therefore, it must be assured that the device is calibrated. Also, enough
volume of solution must be present for an accurate measurement of conductivity. If the experiment is
repeated, 200mL from each solution can be prepared to assure enough volume is present.
Heat developed during dissolution, mixing, dilution can also cause temperature changes which introduces
systematic errors. To eradicate this, solutions can be let to sit and reach thermal equilibrium with
environment after serial dilutions.
Serial dilutions are another main source of error in this experiment. In general, serial dilutions are
systematic error prone since an error done in the beginning is carried through the entire dilution process.
Therefore, volume measurements and mixing during serial dilutions must be done rigorously. The volume
measurements during dilutions were done with glass pipettes and volumetric flasks. Small variations in
volume readings and uncertainty of glassware can cause random errors. Losing a drop during
measurements with glass pipette, expansion of the glassware can produce systematic error. The calibration
of the glassware should be done before experiment and glass pipette must be used carefully to minimize
these errors. Parallax error in volumetric flask readings can also cause systematic error. This error is
reduced by taking measurements at eye level.
Conclusion
In conclusion, data suggests that molar conductivities and limiting molar conductivities of KCl, HCl, KAc
were found as good estimates due to high R2 values and manifestation of expected trends in graphs and
corresponding values such as resistance. The main aim of the experiment was to calculate limiting molar
conductivity and acid dissociation constant for acetic acid. Data also suggests that successful
approximation of these values were achieved due to high correlation in graphs and low error percent in Ka
values. The main limitations of this experiment were reported as limited number of different
concentrations and systematic errors due to conductometer and serial dilutions. The experiment can be
repeated in a more temperature stable environment with more data points or with different solutions to
validate the Λ0 and Ka for acetic acid.

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