STUDENT NAME: Manda Baboolal

STUDENT ID: 816014005

COURSE CODE: CHEM2673
COURSE TITLE: Core Chemistry Laboratory II
LAB PARTNER: Ibrahim Ali
Experiment #7
 Experiment 7A1
Transport Numbers- Hittorf Method

Purpose: To determine the transport numbers of copper and sulphate ions using the Hittorf
Method.
Objectives:
 To make absorbance measurements on copper sulphate solutions using the UV-Vis
spectrometer.
 To determine the concentration of copper of unknown concentration using a calibration
curve.
 To determine the transference number for copper and sulphate ions using the Hittorf
method.

Introduction and Theory

The Hittorf Method measures the ion concentration changes near electrodes. It is based on the
fact that during electrolysis the loss in the amount of electrolyte around any electrode is
proportional to the speed moving away from it. The apparatus in this experiment consists of a
limbed vessel provided with Pt electrodes with a U-tube connected at the middle. This allows for
solution withdrawal. The apparatus is then filled with AgNO3 and is connected in series to a
direct current source. After electrolyzing, the stopcocks are then opened and is then analyzed
with ammonium thiocyanate.
The change in the electrode at the anode is then obtained and analyzed.
To determine the transport number
The negative ions migrate to the cathode and the negative ions migrate to the anode. This is
dependent on its size and charge. Therefore, the total current is given by:
I = I+ + I –
The transference number can be calculated from this since for the positive ion the transference
number can be calculated as:
t+ = I+ / I
t– = I – / I
t+ + t – = 1
 Apparatus and Materials:
As shown in lab handout, Experiment 7A1, Page 4
Procedure:
As shown in lab handout, Experiment 7A1, Pages 4 and 5. However, no practical work was
possible for this experiment in 2020.

Results and Relevant Data Tables

Table 1: Table showing mass of CuSO4.5H2O and the water that was used to prepare the solution
for analysis and its absorbance value.
Sample Mass(g) Absorbance at 720nm.
Mass of CuSO4.5H2O weighed 6.0594 1.313
Mass of H2O weighed 150.0600

Table 2: Table showing mass of CuSO4.5H2O Solutions After Electrolysis & Absorbance of
Solutions at 720 nm.
Compartment Mass of CuSO4.5H2O solution (g) Absorbance at 720nm
Cathode 33.6589 1.284
Anode 34.2944 1.325

Table 3: Table showing mass of CuSO4.5H2O Solutions (Standards) and absorbance of the
solutions at 720nm
Calibration Calibration Calibration Calibration Calibration
Solution 1 Solution 2 Solution 3 Solution 4 Solution 5
Mass of CuSO4.5H2O(g) 0.3002 0.3515 0.4011 0.4511 0.5019
Mass of water used (g) 10.0984 10.0379 10.0025 10.0307 10.0969
Concentration of 0.0297 0.0350 0.0401 0.0450 0.0450
calibration solutions
Absorbance at 720nm 0.957 1.153 1.312 1.474 1.064
Data Analysis
In order to determine the concentration of the Hittorf solutions, a graph of absorbance vs
concentration was plotted:
 Graph showing absorbance vs concentration
1.6
1.4
1.2 f(x) = 19.4773863504244 x + 0.432381932333449
R² = 0.390646036413955
1
Absorbance

0.8
0.6
0.4
0.2
0
0.025 0.03 0.035 0.04 0.045 0.05
Concentration

Table 1: Table showing the concentration of the calibration solutions.

Calibration Solution Concentration
1 0.0270
2 0.0370
3 0.0452
4 0.0535
5 0.0324

Sample calculations:
In order to determine the concentrations of the calibration solutions, the line of the equation
y=mx+c, where y=absorbance, m is the gradient, x is the concentration and c is the intercept.
For calibration solution 1;
when y= 0.957
x= (y-c)/m
x= (0.957-0.4324)/19.477
x= 0.0270
The grams of solution collected from the anode (anolyte) = x= 34.2944 g
Final concentration of CuSO4.5H2O,c = ?
The equation for Beer's law is: A = εmCl to calculate concentration
where :
 A=absorbance (no unit)
 εm = molar extinction coefficient (M−1cm−1)
 C = concentration (M or mol/L)
  l = path length of 1 cm

Recall :

The equation in the form y=mx + b

y = 19.4770x + 0. , Where :
y = absorbance (A)
x = concentration (C)
m = (εm) = slope or the molar extinction coefficient in beers law.
So A = εmC +b

Solving for C (concentration)

C = (A-b)/εm

C = (1.325-0.0238)/ 31.938
C= 0.041 M

Therefore:
c / (c +1) = 0.041/ (0.041 +1 ) = 0.039 grams per gram of solution

cx/(c+1) = (0.041)(34.2944)/ (0.041 + 1 ) = 1.351 grams in collected solution

63.54 (0.041)(34.2944)/ 249.68 (0.041 + 1) = 0.3437 g of Cu collected.

Original solution concentration = (6.0594/ 150.0600)= d= 0.04 grams per gram of water .

So there was 63.54 (0.04) (34.2944) / 249.68 (0.04 +1) =0.3357 grams of Cu in the anode
compartment at the start.

Amount of copper the anode compartment gained during electrolysis.

Z= 0.3437 g - 0.3357 g = 0.008 g

Weight of copper that dissolved from the anode during electrolysis :

Recall : The electrolysis of the CuSO4.5H2O solution was carried out for exactly 60 min at a
current of 8.0 mA

copper (+)  Cu(s) - 2e-   Cu2+(aq) , Atomic mass of copper = 64 g/mol

Current in A x time in secs (Q = I x t)

(0.008 A )x 2 x ( 60 x 60 ) = 57.6 Coulombs and 1 mole electrons = 96500 Coulombs

Therefore moles of electrons passed through circuit = 57.6 / 96500 = 0.0006

 it takes two moles of electrons to dissolve one mole of copper

therefore moles copper = 0.0006 / 2 = 0.0003

mass of copper = moles of copper x atomic mass of copper

= 0.0003 x 64 = 0.0192 g of copper dissolved

Z= 0.008 g
Y= 0.0192 g

The transport number for Cu2+ = (Y- Z) / Y

(0.0192 -0.008) / 0.0192 = 0.583

Cathode compartment .
The grams of solution collected from the cathode = x= 33.6589 g
Final concentration of CuSO4.5H2O ,c =
Apply Beer's law to calculate the concentration.
The equation for Beer's law is: A = εmCl
where :
 A=absorbance (no unit)
 εm = molar extinction coefficient (M−1cm−1)
 C = concentration (M or mol/L)
 l = path length of 1 cm

Recall :

The equation in the form y=mx + b

y = 31.938x + 0.0238 , Where :
y = absorbance (A)
x = concentration (C)
m = (εm) = slope or the molar extinction coefficient in beers law.
So A = εmC +b

Solving for C (concentration)

C = (A-b)/εm

C = (1.284-0.0238)/ 31.938
C= 0.04 M
Therefore:
c / (c +1) = 0.04/ (0.04 +1 ) = 0.038 grams per gram of solution

cx/(c+1) = (0.04)( 33.6589)/ (0.04 + 1 ) = 1.295 grams in collected solution

63.54 (0.04)( 33.6589)/ 249.68 (0.04 + 1) = 0.329g of Cu collected.

Original solution concentration = (6.0594/ 150.0600)= d= 0.04 grams per gram of water .

So there was 63.54 (0.04) (33.6589) / 249.68 (0.04 +1) = 0.329 grams of Cu in the cathode
compartment at the start .

Amount of copper the anode compartment gained during electrolysis.

Z= 0 .329 g – 0.329 g = 0 g

Weight of copper that dissolved from the anode during electrolysis :

Recall : The electrolysis of the CuSO4.5H2O solution was carried out for exactly 60 min at a
current of 8.0 mA

copper (-) Cu2+(aq) + 2e-   Cu(s), Atomic mass of copper = 64 g/mol

Current in A x time in secs (Q = I x t)

(0.008 A )x 2 x ( 60 x 60 ) = 57.6 Coulombs and 1 mole electrons = 96500 Coulombs

Therefore moles of electrons passed through circuit = 57.6 / 96500 = 0.0006

it takes two moles of electrons to dissolve one mole of copper

therefore moles copper = 0.0006 / 2 = 0.0003

mass of copper = moles of copper x atomic mass of copper

= 0.0003 x 64 = 0.0192 g of copper lost

Z= 0.008 g
Y= 0.0192 g

The transport number for Cu2+ = (Y- Z) / Y

(0.0192 -0.008) / 0.0192 = 0.583

Transport number of SO42- = 1- 0.583 = 0.417

Pre-lab exercises
 1. Ion transport or transference number refers to the fraction of the total electrical current
carried by an electrolyte from a given ionic species.
2. (i)An important property of electrolytic solutions that can be obtained from transport
numbers is that it tells us the electrical mobility of the ions in solution. Different ions have
different transport numbers, and ions that carry less current move slower than those that
have a higher current.
(ii)Two additional properties of an electrolyte that can be obtained from electrical mobility
is the type of electrolyte used (strong or weak) and its concentration in an electrolytic
solution.
3. To find the equivalent conductance of BaCl2:
BaCl2= molecular weight/2
Λo for BaCl2= Λo Ba2+ + 2ΛoCl-
Λo for BaCl2 = 1/2 Λo Ba2+ + Λo Cl-
= 1/2(0.0127) + 0.00763
Λo for BaCl2 = 0.01398 Ω-1 m2 mol-
t+ = λBa2+ / λBaCl2
t+ = 0.0127/0.01398
t+ = 0.091

t+ + t- = 1
t- = 1 – t+
t- = 1 – 0.91
t- = 0.09

Post Lab Exercises:

2. Ionic mobility is the ability of charged particles to move through a medium in response to an
electric field pulling them.
In order to find the mobility of an ion, the formula is used:

Where E is the magnitude of the applied electric field, vd is the velocity and µ is the ionic
mobility.
3. In order to achieve accurate readings, calibrating the spectrophotometer allows more accurate
value measurements. When the spectrophotometer is turned on, allow it to warm up at a
minimum of 10 minutes. The desired wavelength at which the solutions to be measured is
changed on the chamber. A blank solution of solvent should be prepared by filling the cuvette up
to the mark. The cuvette should be properly washed with deionized water to avoid
contamination. The clear sides of the cuvette should be wiped to remove any fingerprints and
other materials on the cuvette. Place the blank on the cuvette holder labelled for the blank, close
the lid and set the adjustment to zero. Remove the blank and the samples to be analyzed can then
be placed one by one into the designated groove. Ensure that all cuvettes are wiped properly and
that separate droppers should be used for each cuvette to avoid cross contamination. Press the
read button on the meter and wait for the reading to stabilize before recording.

References
https://chem.libretexts.org/Bookshelves/Inorganic_Chemistry/
Modules_and_Websites_(Inorganic_Chemistry)/Chemical_Reactions/Chemical_Reactions_1/
Electrolytes
 Experiment 7A2

Purpose: To determine the transport number of the hydrogen cation in a solution of HCl using
the moving boundary method.

Objectives
 To determine the transference number for aqueous H+ ion relative to the Cl- ion using the
moving boundary method.
 To determine the transport number of H+ ion from a linear plot of transport number
equation.

Introduction
The moving boundary method is used to determine the transference number of ions. In this
experiment, the transport number of H+ and Cl- ions will be determined via the moving
boundary method using a HCl solution. During this method, an applied electric field causes
movement of the boundary of the two adjacent electrolytes. The cation in the indicator
electrolyte moves slower than the cation in which its transport number is to be determined, which
is the H+ ion. In the moving boundary method, CdCl2 rods is the most appropriate because the
Cd2+ ions are less mobile than the H+ ions and they both have the Cl- ion in common.
The anode compartment to this was the cadmium rods while the cathode consists of Ag/AgCl
compartment. A solution of cadmium chloride is formed near the anode since it consists of
cadmium and then migrates towards the cathode. Methyl orange or bromophenol blue indicators
can be added which makes the boundary visible between the HCl and CdCl2 solution. HCl
therefore has a higher conductivity than cadmium chloride and the boundary remain sharp.
Theory
The total charge passing through the solution is given by the symbol Q. Therefore, to determine
the transference number of the hydrogen ion with a charge of Q+
t+ = Q+/Q
Since current is Q=It, then the charge carried out by the H+ ions is
Q+=FNV
where F is Faraday's constant, n is the number of moles and V is the volume swept out
The transference number can then be calculated using the equation:
t+ = FNV/It

Apparatus and Materials: As shown in Experiment 7A2 lab handout, pages 5 and 6.
Procedure: As shown in the Experiment 7A2 lab handout, page 7.
Results and Relevant Data Tables
Table 1: Table showing Volume-Time measurements at 1.0 mA for 0.02M HCl solution.
Volume(mL) Time(s)
0.95 0
0.90 105
0.85 210
0.80 317
0.75 425
0.70 524
0.65 635
0.60 734
0.55 842
0.50 950
0.45 1053
0.40 1152
0.35 1263
0.30 1366
0.25 1475
0.20 1576
0.15 1684
0.10 1796
0.05 1893
0.00 2004
Table 2: Table showing volume-time measurements at 0.6mA for 0.01M HCl solution.
Volume (mL) Time(s)
0.95 0
0.90 87
0.85 176
0.80 266
0.75 350
0.70 434
0.65 524
0.60 606
0.55 694
0.50 783
0.45 870
0.40 955
0.35 1044
0.30 1128
0.25 1215
0.20 1300
0.15 1387
0.10 1472
0.05 1561
0.00 1645
 Data Analysis
Graph 1: Graph showing the volume swept out against time in seconds at 1.0 mA for 0.02M HCl
solution.

Graph showing Volume swept out (mL) against Time(s) for 0.02M
HCl
1

0.9 f(x) = − 0.000474826853381626 x + 0.949921818752303

R² = 0.999978212968271
0.8

0.7

0.6
Volume(mL)

0.5

0.4

0.3

0.2

0.1

0
0 500 1000 1500 2000 2500

Time(s)

To calculate the transport number for H+ ion

Since the slope of the graph is V/t
Graph 2: Graph showing volume swept out against time 0.6mA for 0.01M HCl solution.

Graph showing Volume swept out (mL) against Time (s) for 0.01M
HCl.
1

0.9 f(x) = − 0.000577786250483455 x + 0.951586988711278

R² = 0.99998726205853
0.8

0.7

0.6
Volume(mL)

0.5

0.4

0.3

0.2

0.1

0
0 200 400 600 800 1000 1200 1400 1600 1800

Time(s)
 Experiment 7B
Conductometric Titrations

Purpose: To use conductance measurements to determine the equivalence point of acid-base

reactions.
Objectives:
-To determine the equivalence point of acid-base conductance titrations.
-To compare between conductance equivalence point and the indicator end point.
- To compare between the conductance equivalence point and its theoretical equivalence point.

Introduction and Theory

Conductometry is a measure of chemical reactions by its electrical conductivity. It is usually
done in the form of titrations, which monitors the electrical conductivity of the reacting mixture.
This is known as conductometric titrations. The principle is based on one of the ions replacing
another and since ionic conductivity of each is different results in a change in its conduction
during the titration. In this experiment four titrations are done with acid-base reactions. They
include:
1.Strong acid- Weak base - for example H2SO4 and NH3. Gradually over time the conductivity
of the solution decreases due to the replacement of the H+ ions on addition of sulphuric acid. The
graph levels off past the endpoint because the excess ammonia will not be ionized due to
ammonia sulphate present. The following graph shows the titration for strong acid weak base and
its endpoint.
2. Strong base-weak acid- for example NaOH and acetic acid. The conductance is low initially,
and then further decreases as we add NaOH. This is accounted for by the replacement of the H+
ions by Na+ and due to the common ion of acetate. After some time, the conductance will start to
increase as the sodium hydroxide neutralizes the acetic acid. This will then increase up to the
equivalence point and will then curve due to the presence of sodium acetate. Beyond the
equivalence point it is expected that the conductance will continue to increase due to the
presence of extra OH- ions. The following graph shows the titration for a strong base weak acid
and its equivalence point.

4.Weak acid- weak base- e.g. acetic acid and ammonia. This is like a weak acid strong base
titration. After the equivalence point is reached, conductance remains the same as the ammonia is
constantly ionized. The following graph shows the titration for a weak acid weak base and its
equivalence point.
4. Strong acid-strong base - for example NaOH and HCl. Due to presence of HCl which is a
source of H+ ions, the conductivity will therefore be high. On addition of the NaOH, we would
see that conductivity will start decreasing and will continue until the equivalence point is
reached. Past this we would observe an increase in conductivity as the OH- ions in the solution
increases.
The graph below shows the titration for a strong acid and strong base and its equivalence point.

Apparatus and Materials: As shown in Experiment 7B handout, page 2

Procedure: As shown in Experiment 7B lab handout, page 3. However, no practical was
possible for this experiment in the academic year 2019/2020.

Results and Relevant Data Tables.

Table 1: Table showing titration of NaOH and HCl (strong acid-strong base) using
Methyl red indicator.
Volume of 1.0M Volume of Conductivity (μS) Conductivity Color Change
HCl added (mL) 1.0M HCl (L) (S)
0.00 0.00 828 0.000828
0.20 0.0002 747 0.000747
0.40 0.0004 666 0.000666
0.60 0.0006 566 0.000566
0.80 0.0008 477 0.000477
1.00 0.0010 456 0.000456
1.20 0.0012 753 0.000753 Pink to
colorless
 1.40 0.0014 1071 0.001071
1.60 0.0016 1450 0.001450
1.80 0.0018 1790 0.001790
2.00 0.0020 2190 0.002190

Table 2: Table showing titration between NaOH and Acetic acid (strong base-weak acid)
using phenolphthalein indicator.
Volume of 1.0M Volume of Conductivity (μS) Conductivity Color Change
HCl added (mL) 1.0M HCL(L) (S)
0.00 0.0000 808 0.000808
0.20 0.0002 698 0.000698
0.40 0.0004 593 0.000593
0.60 0.0006 486 0.000486
0.80 0.0008 374 0.000374
1.00 0.0010 316 0.000316
1.20 0.0012 313 0.000313 Pink to colorless
1.40 0.0014 312 0.000312
1.60 0.0016 311 0.000311
1.80 0.0018 311 0.000311
2.00 0.0020 311 0.000311

Table 3: Table showing titration between acetic acid and ammonia (weak acid-weak
base) using methyl red indicator.
Volume of 1.0M Volume of Conductivity (μS) Conductivity Color Change
HCl added (mL) 1.0M HCl(L) (S)
0.00 0.0000 344 0.000344
0.60 0.0006 808 0.000808
1.20 0.0012 1426 0.001426
1.80 0.0018 2290 0.002290
2.40 0.0024 2980 0.002980 Red to colorless
2.82 0.00282 3350 0.003350
3.60 0.0036 3340 0.003340
4.20 0.0042 3330 0.003330
4.80 0.0048 3320 0.003320
5.40 0.0054 3300 0.003300
6.00 0.0060 3290 0.003290
 Table 4: Table showing titration between sulphuric acid and ammonia (strong acid-weak
base) using methyl red indicator.
Volume of 1.0M Volume of Conductivity (mS) Conductivity Color Change
HCl added (mL) 1.0M HCl(L) (S)
0.00 0.0000 12.07 0.01207
0.80 0.0008 10.45 0.01045
1.60 0.0016 8.75 0.00875
2.40 0.0024 7.26 0.00726
3.20 0.0032 6.02 0.00602
3.76 0.00376 5.33 0.00533 Red to colorless
4.80 0.0048 5.33 0.00533
5.60 0.0056 5.31 0.00531
6.40 0.0064 5.28 0.00528
7.20 0.0072 5.25 0.00525
8.00 0.0080 5.22 0.00522

Data Analysis
To calculate the theoretical equivalence point:
1. For strong acid strong base reaction:

NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(aq)

From the information provided, there is 100mL of NaOH of concentration 0.01M and
10mL of HCl of 1.0M.
To calculate the volume at the equivalence point:

Step 1: Calculate the number of moles of NaOH

n = cxv
n = 0.01 mol L-1 x 0.1L
n= 0.001 mol
At the equivalence point the number of moles of acid=moles of base
Therefore the number of moles of HCl= 0.001mol
The volume of acid required to reach equivalence point:
v = n/c
v = 0.001mol/1.0mol L-1
v = 0.001 L-1
 v = 1 mL

2. For strong base - weak acid reaction:

NaOH(aq) + CH3COOH(aq)  CH3COONa(aq) + H2O(aq)

From the information provided, there is 100mL of NaOH of concentration 0.01M and
10mL of CH3COOH of 1.0M.
To calculate the volume at the equivalence point:

Step 1: Calculate the number of moles of NaOH

n = cxv
n = 0.01 mol L-1 x 0.1L
n= 0.001 mol
At the equivalence point the number of moles of acid=moles of base
Therefore the number of moles of CH3COOH = 0.001mol
The volume of acid required to reach equivalence point:
v = n/c
v = 0.001mol/1.0mol L-1
v = 0.001 L-1
v = 1 mL

3. For weak base – weak acid reaction:

CH3COOH(aq) + NH3(aq)  CH3COO-(aq) + NH4+(aq)

From the information provided, there is 100mL of CH3COOH of concentration 0.03M
and 10mL of 1.0M NH3.
To calculate the volume at the equivalence point:

Step 1: Calculate the number of moles of CH3COOH

n = cxv
n = 0.03 mol L-1 x 0.1L
n= 0.003 mol
At the equivalence point the number of moles of acid=moles of base
Therefore the number of moles of NH3 = 0.003mol
The volume of base required to reach equivalence point:
v = n/c
v = 0.003mol/1.0mol L-1
v = 0.003 L-1
v = 3 mL
 4. For strong acid – weak base reaction:

H2SO4(aq) + 2NH3(aq)  (NH4)2SO4(aq)

From the information provided, there is 100mL of H2SO4 of concentration 0.02M and
10mL of 1.0M NH3.
To calculate the volume at the equivalence point:

Step 1: Calculate the number of moles of H2SO4

n = cxv
n = 0.02 mol L-1 x 0.1L
n= 0.002 mol
Since there are 2 moles of NH3
n = 0.004mol
At the equivalence point the number of moles of acid=moles of base
Therefore the number of moles of NH3 = 0.004mol
The volume of base required to reach equivalence point:
v = n/c
v = 0.004mol/1.0mol L-1
v = 0.004 L-1
v = 4 mL

Question 2: To determine the experimental equivalence point, graphs for each titration were
plotted and the equivalence point was obtained.

Graph 1: Graph showing the conductance vs volume for strong acid HCl and strong base NaOH
titration and its equivalence point.

Graph showing the equivalence point of NaOH and

HCl titration
2500

2000
Cnnductance(μS)

1500

1000

500

0
0 0.5 1 1.5 2 2.5
Volume(mL)
Equivalence point: Volume: 1.0mL and a conductance of 456 μS.

Graph 2: Graph showing the conductance vs volume for strong base, NaOH and weak acid, acetic
acid titration and its equivalence point.

Graph showing the equivalence point of titration with NaOH

and acetic acid
900
800
Conductance(μS)

700
600
500
400
300
200
100
0
0 0.5 1 1.5 2 2.5
Volume(mL)
Equivalence point: Occurs at a volume of 1.0mL and a conductance of 316.

Graph 3: Graph showing the conductance vs volume for strong base, NaOH and weak acid,
acetic acid titration and its equivalence point.

Graph showing the equivalence point of titration with acetic

acid and ammonia.
4000

3500

3000
Conductance(μS)

2500

2000

1500

1000

500

0
0 1 2 3 4 5 6 7

Volume(mL)
Equivalence point= Occurs at a volume of 2.82mL at a conductance of 3350 micro siemens.

Graph 4: Graph showing the conductance vs volume for weak base, ammonia and strong acid,
sulphuric acid titration and its equivalence point.

Graph showing the equivalence point of titration with

sulphuric acid and ammonia
14

12

10
Conductance(mS)

0
0 1 2 3 4 5 6 7 8 9
Volume(mL)
Equivalence point: Occurs at a volume of 3.76mL and a conductance of 5.33mS.

Pre- Lab Questions;

1. The limitations in an indicator titration experiment includes:
- The end point and the equivalence point are not the same.
- The level of uncertainty for each measurement such as pipettes and burettes which may have ±
0.1 mL of the true value.
-Human error such as overshooting, parallax errors and contamination of pipettes and burettes.
2. The advantages of using conductivity measurements to determine the equivalence point of
acid base titrations is that it can be used with
-Weak acids and very diluted solutions.
- Solutions in which the end point cannot be seen with the naked eye.
-It gives a more accurate end point.

Post-Lab Questions
1. The possible sources of error include:
- Failure to titrate beyond the equivalence point. If this is not done, then it would be impossible
to determine the equivalence point.
- Not mixing the solution during the titration, this will not allow the acid and base solutions to
properly interact and react and will slow down product formation.
-Not flushing the titrator will cause contamination of the solution resulting in deviation of the
equivalence point from the theoretical and resulting in dilution of the solution.
2. For the strong acid, strong base titration it was observed that the theoretical and experimental
equivalence point were the same (1.0mL). This means that there were no sources of error that
would cause values to deviate from the theoretical value.
For the strong base, weak acid titration the theoretical and experimental equivalence point was
also found to be 1.0 mL. This also indicates that during this titration, no experimental or human
error may have occurred to allow the experimental to be the same as the theoretical value.
For the weak base, weak acid titration, the theoretical equivalence point was 3mL while the
experimental was found to be 2.82mL. This is not a significant difference from the theoretical
and can be due to errors such as dilution causing the experimental value to be lower.
For the strong acid, weak base titration, the theoretical equivalence point was calculated to be
4mL while the experimental was found to be 3.76mL.

3. The concentration in the burette is higher than that in the beaker to keep volumes changes as
minimum as possible.
4. In Figure one, shows the graph for a strong acid strong base titration. We observe that as the
volume increases initially, the conductivity decreases rapidly. The initial high conductance is due
to the presence of the H+ ions and as we continually add base, the conductance decreases. The
point at where the two lines intersect is known as the equivalence point where the number of
moles of acid and base are the same. As more base is being added into the solution, we will see
the conductivity rapidly increasing again hence the other line that goes up.
Figure two shows the titration graphs for weak acid and strong base as well as for strong acids
and weak bases. Gradually the conductance decreases with increasing volume due to the
replacement of H+ ions on addition to the base. The graph eventually levels off (where the
straight line is seen) because no ionization occurs at this point. The point at where the two lines
intersect is known as the equivalence point.
Figure three shows the titration graph for weak acid, weak base titration. Initially we see that the
conductivity is low at first but then gradually increases as we add more base. The graph then
levels off and where the two lines intersect gives us the equivalence point.
 References
https://education.seattlepi.com/limitations-titration-experiments-7070.html

https://salve.digication.com/alexanderantonopoulos/Lab_26_Conductometric_Titration

https://www.quora.com/What-are-the-advantages-of-conductometric-titrations
 Experiment 7C
The Glass Electrode- Potentiometric Titrations
Purpose: To illustrate the use of the potentiometer as an instrument for the measurement of the
electromotive force (EMF) of an electro-chemical cell, and the application of the information so
obtained to the determination of the endpoint of a titration.
Objectives:
- To determine the end point of an oxidation-reduction titration (potassium permanganate and
ferrous ammonium sulphate).
-To determine the end point of an acid-base titration (sodium hydroxide with hydrochloric acid).

Introduction
Potentiometric titration involves the use of an electrolyte solution to characterize an acid without
the use of an indicator. The two main electrodes used are the glass electrode and a reference
electrode. There are four main types of potentiometric titrations:
-Acid base titrations
-Redox titrations
-Precipitation titrations
-Complexometric titrations.
The indicator electrode is used to form an electrochemical half-cell while the reference forms the
other half.
The glass electrode can be used for pH measurements. The indicator electrode contains a pH
sensitive glass membrane and a small amount of HCl with saturated AgCl is contained in the
tube. The silver wire in the solution forms an Ag/AgCl inner reference electrode, which connects
to the pH meter. The electric potential created between the glass electrode and the inner
reference electrode give us the pH value.
In potentiometric titrations, the cell potential is recorded after adding a certain volume of titrant.
Theory
The cell for potentiometric analysis is represented by the equation:
Ecell= Eind – Eref + Ej
Where Eref is the reference electrode, Ej is the salt bridge and Eind is the indicator electrode.

In order to determine the end point of a potentiometric titration, a plot of potential against
volume can be used according to the graph below:

Apparatus and Materials: As shown in Lab Handout Experiment 7C, Page 3

Procedure: As shown on lab handout, Experiment 7C, Page 4. However, no practical lab
exercises were possible for this experiment.
 Results and Relevant Data Tables.
Oxidation-Reduction Titration
Preparation of 50 mL of an approx. 0.01 M KMnO4 Solution
Mass of solid KMnO4 weighed = 0.07982 g

Preparation of 50 mL of an approx. 0.02 M Solution of (NH4)2SO4.FeSO4.6H2O

Mass of solid (NH4)2SO4.FeSO4.6H2O weighed = 0.3872 g
Table 1: Table showing Titration between KMnO4 (0.01M) and (NH4)2SO4.FeSO4.6H2
Volume of KMnO4 added(mL) EMF(mV)
0.00 280.2
1.00 275.8
2.00 274.8
3.00 276.5
4.00 279.9
5.00 281.0
6.00 286.1
7.00 292.6
8.00 299.7
9.00 303.7
10.00 307.2
11.00 397.6
12.00 609.1
13.00* 974.8
14.00 1007.8
15.00 1035.5
16.00 1047.7
17.00 1057.1
18.00 1066.2
18.50 1071.9
19.00 1076.9
19.50 1079.9
20.00 1083.5
20.50 1086.1
21.00 1088.7
*Solution changed from colorless to pink
Table 2: Table showing titration between NaOH (0.1M) and HCl (0.1M) using methyl orange
indicator.
Volume of HCl added(mL) pH Volume of HCl added (mL) pH
0.00 13.09 0.50 11.79
1.00 13.05 0.50 11.70
1.00 13.02 0.50 11.58
1.00 12.99 0.50 11.43
1.00 12.95 0.20 11.35
1.00 12.92 0.10 11.31
1.00 12.88 0.10 11.26
1.00 12.85 0.10 11.20
1.00 12.81 0.10 11.14
1.00 12.78 0.10 11.06
1.00 12.74 0.10 10.97
1.00 12.70 0.10 10.86
1.00 12.66 0.10 10.70
1.00 12.62 0.10 10.45
1.00 12.58 0.10 9.84
1.00 12.53 0.10 3.67
1.00 12.49 0.10* 3.37
1.00 12.44 1.00 2.60
1.00 12.38 1.00 2.34
1.00 12.32 1.00 2.19
1.00 12.26 1.00 2.08
1.00 12.18 1.00 1.99
0.50 12.14 1.00 1.92
0.50 12.10 1.00 1.87
0.50 12.06 1.00 1.82
0.50 11.99 1.00 1.78
0.50 11.94 1.00 1.74
0.50 11.87

Data Collection and Analysis

1. Graph showing the end point the titration reaction between KMnO4 (0.01M) and
(NH4)2SO4.FeSO4.6H2.
End Graph showing the relationship between EMF(mV) and
Volume(mL)
1200

1000

800
EMF (mV)

600

400

200

0
0 5 10 15 20 25 30
Volume(mL)

point = 12.00mL

Graph 2: Graph showing the end point between NaOH (0.1M) and HCl (0.1M) using methyl
orange indicator.

Graph showing the pH vs the volume of the solution

14

12

10

8
pH

0
0 10 20 30 40 50 60
Volume(ml)

End point – 0.1mL.

1. 2. For the titration between KMnO4 (0.01M) and (NH4)2SO4.FeSO4.6H2 it was seen from
the graph that the end point was found to be at 12.00mL. Compared to the visual color
change which was at 13.00mL, it is seen that the difference between these two methods
are not large and differ by a volume by 1.0mL. This can be due to the type of indicator
used which produces a color change at a certain pH, causing it to have a higher volume at
the visual end point.
For the reaction between NaOH and HCl the graphical end point was found to be 0.1mL
while the visual method was also at 0.1mL. Since endpoint reactions for color changes
are relatively dependent on pH, the graphical and visual method will be the same.

Pre-Lab Exercises
1. Electrode potential is known as the potential of a cell consisting of the electrode to be
determined that acts as the cathode and the reference electrode acting as the anode.
Redox potential on the other hand, is a measure of a chemical species to gain or lose
electrons to an electrode and be oxidized or reduced and is measured in volts (V).

2. The Nernst equation is given by the formula:

Ecell = Eocell – (RT/nF) lnQ
where Ecell is the cell potential
Eocell is the standard cell potential
R is the universal gas constant, 8.314J K-1 mol-1.
T is the temperature in kelvin
n is the number of moles
F is Faraday’s constant = 96485 C mol-1
and Q is the reaction quotient.

3. The cell reaction for this will be:

Ni + Cu2+  Ni2+ + Cu Eocell = ?
Therefore the cathodic half reaction will be:
Cu2+ + 2e-  Cu Ecell = +0.34
The anodic half reaction is:
Ni  Ni2+ + 2e- Ecell = +0.26
To calculate the cell potential for the overall reaction:
Eocell = Eocell(cathode) - Eocell(anode)
Eocell = +0.60V.
Using the Nernst equation:
Ecell = Eocell – (RT/nF) ln (aNi2+ / aCu2+)
Ecell = +1.35V.
 4. To calculate pH, the expression is used as shown below:
pH= -log[H+]

5. To calculate the pH of 0.1M NaOH

.Poh= -log [OH-]
Since 1 mol NaOH produces 1 mol OH- ions
[OH-] = 0.1
Poh = -log (0.1) = 1
We know that pH+pOH=14
Ph=14-Poh
=14-1
=13

Post Lab Questions

1. The dissociation of a weak acid (represented by HA) in water can be described by

HA⇌H+ + A−
Ka=[H+] [A−]/[HA]
In order to determine the dissociation constant, the unknown sample is weighed in a
100mL break and dissolved in 50mL of water. It will then be transferred to a clean
200mL volumetric flask and diluted to the mark. 25mL of water and 50mL of the solution
is put into a beaker. A pH meter is then submerged into solution and then titrated with
NaOH. The pH is then recorded for every 1.0mL of NaOH added. A titration curve is
then plotted. The endpoint is determined and is used to calculate the molecular weight of
the unknown (since moles of acid=moles of base). Since the pH=pKa, then ka can easily
be calculated.

References

https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/
Supplemental_Modules_(Analytical_Chemistry)/Analytical_Sciences_Digital_Library/JASDL/
Courseware/Analytical_Electrochemistry%3A_Potentiometry/06_Experiments/
01_Potentiometric_Titration_of_an_Unknown_Weak_Monoprotic_Acid