Lecturer: Assoc. Prof.

Ngo Van Tu Student: Nguyen Thi Thanh Tam

HUE’S UNIVERSITY
HUE’S UNIVERSITY OF EDUCATION
CHEMISTRY DEPARTMENT
--------------

ESSAY
UNIT OF STUDY: PHYSICAL CHEMICAL ANALYSIS
AND TREATMENT OF EXPERIMENTAL DATA
TOPIC: EXERCISES ABOUT COULOMETRIC
METHODS

Instruction Lecturer: Student:

Assoc. Prof. Ngo Van Tu Nguyen Thi Thanh Tam
Class : Chemistry 3E
Student’s code: 16S2011055
School year: 2018-2019
Hue, May 2019
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

ACKNOWLEDGEMENT
A completed study would not be done without any assistance. Therefore, the
author who conducted this essay gratefully gives acknowledgement to their support
and motivation during the time doing this essay: “EXERCISES ABOUT
COULOMETRIC METHODS”
On my honor, I would first like to express my endless thanks and
respectfulness to my supervisor Associate Professor Dr. Ngo Van Tu. His kindly
support and continuous advices went through the process of studying, researching and
completing my topic. I would also like to sincerely thank the teachers in the Faculty of
Chemistry at Hue University’s College of Education for their help and guidance during
the past time. I also acknowledge my thankfulness to all fellow students. Without their
encouragement and enthusiastic support, my essay would have been impossible to be
done effectively.
Although I have constantly tried to improve the essay, it is inevitable to have
mistakes due to limited knowledge and English ability. I am looking forward to
receiving comments from you and others so that my knowledge in this field could be
improved.
I sincerely thank you all.
Hue, May 2019
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

TABLE OF CONTENTS

PART 1: BEGINNING ....................................................................................................1

I. Reasons for choosing this topic ................................................................................1
II. Research Purposes ...................................................................................................1
III. Research tasks .......................................................................................................1
IV. Objects of study .....................................................................................................1
V. Methods for study....................................................................................................2
PART 2: CONTENTS ....................................................................................................3
Exercise 1: ....................................................................................................................3
Exercise 2: ....................................................................................................................4
Exercise 3: ....................................................................................................................4
Exercise 4: ....................................................................................................................6
Exercise 5: ....................................................................................................................6
Exercise 6: ....................................................................................................................7
Exercise 7: ....................................................................................................................9
Exercise 8: ..................................................................................................................10
Exercise 9: ..................................................................................................................10
Exercise 10: ................................................................................................................12
Exercise 11: ................................................................................................................13
Exercise 12: ................................................................................................................14
Exercise 13: ................................................................................................................15
Exercise 14: ................................................................................................................17
Exercise 15: ................................................................................................................19
Exercise 16: ................................................................................................................20
Exercise 17; ................................................................................................................21
Exercise 18: ................................................................................................................22
Exercise 19: ................................................................................................................23
Exercise 20: ................................................................................................................24
PART 3: CONCLUSIONS...........................................................................................27
REFERENCE MATERIALS ........................................................................................28
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

PART 1: BEGINNING

I. Reasons for choosing this topic

Coulometry is based on an exhaustive electrolysis of the analyte. By exhaustive
we mean that the analyte is completely oxidized or reduced at the working electrode or
that it reacts completely with a reagent generated at the working electrode. There are
two forms of coulometry: controlled-potential coulometry, in which we apply a
constant potential to the electrochemical cell, and controlled-current coulometry, in
which we pass a constant current through the electrochemical cell. For this reason,
Coulometric method is a useful quantitative method of electrochemical analysis
methods in modern analytical method .
Therefore, I have carried out the topic: " EXERCISES ABOUT
COULOMETRIC METHODS” with the desire to provide a useful reference to
teachers and students.
This topic also helps students, students to learn, reference exercises or in
reference books of foreign countries. Hopefully this topic is a useful document for
readers who are interested in studying chemistry.
Thank you sincerely
II. Research Purposes
- Promoting my ability to explore, learn myself. From that, building good
exercises for students.
- Synthesizing exercise-system to improve knowledge and skill solving it for
students at the university.
- Learn more deeply about analytical exercises, especially electrolytic analysis
methods.
- Approaching the method of solving electrochemical analysis exercises of some
countries in the world.
III. Research tasks
Search and synthesized chemically some exercises electrochemical analysis by
electrolysis of our country and other countries.
IV. Objects of study
Exercises about electrochemical methods of analysis :

1
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Electrolysis (electrogravimetric and coulometric methods)
V. Methods for study
Based on the knowledge learned, conduct searches, research, analyze, compare
and synthesize sources: textbooks of our country and other countries, the examination
questions, etc.

2
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

PART 2: CONTENTS

Exercise 1:
To analyze a brass alloy, a 0.442-g sample is dissolved in acid and diluted to
volume in a 500-mL volumetric flask. Electrolysis of a 10.00-mL sample at –0.3 V
versus a SCE reduces Cu2+ to Cu, requiring a total charge of 16.11 C. Adjusting the
potential to –0.6 V versus a SCE and completing the electrolysis requires 0.442 C to
reduce Pb2+ to Pb. Report the %w/w Cu and Pb in the alloy.

Solution

The reduction of Cu2+ to Cu requires two electrons per mole of Cu (n = 2). We

calculate the moles and the grams of Cu in the portion of sample being analyzed.

Q 16.11C
N Cu   
 8.348 105 mol Cu
nF 2 mol e 96487C

mol Cu mol e
63.55g Cu
8.348 105 mol Cu   5.301103 g Cu
mol Cu

This is the Cu from a 10.00 mL portion of a 500.0 mL sample; thus, the %w/w copper
in the original sample of brass is

500.0 mL
5.301103 g Cu 
10.00 mL
100  60.0%w / w Cu
0.442 g sample

For lead, we follow the same process, thus

Q 0.422 C
N Pb   
 2.19 106 mol Pb
nF 2 mol e 96487C

mol Pb mol e 
207.2 g Pb
2.19 106 mol Pb   4.53 10 g Pb
mol Pb
500.0 mL
4.53 104 g Pb 
10.00 mL
100  5.12%w / w Pb
0.442 g sample

3
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Exercise 2:
The purity of a sample of Na2S2O3 was determined by a coulometric redox
titration using I- as a mediator, and I3- as the “ titrant”. A sample weighing 0.1342
g is transferred to a 100-mL volumetric flask and diluted to volume with distilled
water. A 10.00-mL portion is transferred to an electrochemical cell along with 25
mL of 1M KI , 75 mL of a pH 7.0 phosphate buffer, and several drops of a starch
indicator solution. Electrolysis at a constant current of 36.45 mA required 221.8 s
to reach the starch indicator end point. Determine the purity of the sample.

Solution:

The coulometric titration of S2O32 with I 3 is :

2S2O32 (aq)  I 3 (aq) S 4O62 (aq)  3I  (aq)

Oxidizing S2O32 to S4O62 requires one electron per S2O32 ( n=1).

Solving for the grams of Na2S2O3 gives

ItANa2 S2O3 0.03645  221.8 158.1

mNa2 S2O3    0.01325 g
nF 1 96487

This represents the amount of Na2S2O3 in a 10.00-mL portion of a 100-mL of

the sample, thus 0.1325 g of Na2S2O3 is present in the original sample. The
purity of the sample, therefore, is

0.1325 g Na2 S 2O3

%mNa2 S2O3  100  98.73%
0.1342 g  sample

Note that the calculation is worked as if is S2O32 oxidized directly at the working
electrode instead of in solution.

Exercise 3:
Suppose we wish to electrolyze I  to I3 in a 0.10 M KI solution containing 3.0

×10-5 M I3 at pH 10.00 with fixed at 1.00 bar.

4
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
(a) Find the cell voltage if no current is flowing.

(b) Then suppose that electrolysis increases [ I3 ]s to 3.0 ×10-4 M, but other
concentrations are unaffected. Suppose that the cell resistance is 2.0 Ω, the current
is 63 mA, the cathode overpotential is 0.382 V, and the anode overpotential is 0.025
V. What voltage is needed to drive the reaction?

Solution:

(a) The open-circuit voltage is E(cathode)- E(anode):

Cathode : 2H 2O + 2e  H 2 (g) + 2OH  E o  0.828 V

Anode : I3  2e  3I  E o  0.535 V
0.05916
E(cathode)  0.828  log( PH2 [OH  ]2 )
2
log[ 1.00  1.0  104   =0.591 V
0.05916 2
 0.828 
2  
0.05916  [I  ]3 
E  anode  = 0.535  log   
2  [I3 ] 
0.05916  [0.10]3 
 0.535  log  5 
=0.490 V
2  [3.0 10 ] 
E= E  cathode   E  anode  = 1.081 V

We would have to apply 1.081 V to force the reaction to occur.

(b) Now E(cathode) is unchanged but E(anode) changes because [I3 ]s is different

from [I3 ] in bulk solution.

0.05916  [I  ]3 
E  anode   0.535  log   
2  [I3 ] 
0.05916  [0.10]3 
 0.535  log  4 
=0.520 V
2  [3.0 10 ] 
E  E  cathode   E  anode   IR  overpotentials
 0.591 V  0.520 V  (2.0 )(0.063A)  0.382 V
  1.644 V
Instead of 1.081 V, we need to apply 1.644 V to drive the reaction.

5
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Exercise 4:
Prepare 0.125 g of an alloy sample with 100 ml of H2SO4 to dissolve the sample
completely. Here iron is transferred into solution in the form of Fe2+. Transfer the
whole solution to the electrolyte flask.

Add 50,00 ml of Ce (III) 0,0400M solution. Electrolysis with current intensity I =

0.0500A using Pt electrode. The titration stop is achieved after 511.2 seconds.
Calculate the% Fe content in the alloy.

Solution:

When electrolysis occurs oxidation of Fe2+ at anot:

Fe2+  Fe3+ +e

At the end of electrolysis, Ce3+ oxidation will occur :

Ce3+  Ce4+ +e

Ce4+ produces Fe2+ oxidation:

Ce4+ + Fe2+  Ce3+ + Fe3+

And when Fe2+ is completely finished, a small amount of Ce4+ electrolyte will soar and
we can end electrolysis.

AIt 55.85
mFe    0.050  511.2  0.01479 gam
n  96500 1 96500
0.01479
% Fe  100  12.17%
0.1215

Exercise 5:
To determine the antimony in Sb2O3 form in the analytical sample, we weigh 15
grams of sample and acidify with HCl to obtain the solution. In addition to the
solution, obtain an excess of NaBr solution and then quantify antimony by
titration with the constant current I, knowing that when conducting electrolysis
with a flow of 2.4125 mA for a period of 12 minutes .

a. Write the reaction occurs.

6
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

b. Calculate Sb2O3 content in ppm units. Given that: MSb2O3  291.5

Solution:

The reaction occurs when sample dissolution:

Sb 2O3  12HCl  2H3[SbCl6 ]  3H 2O (1)

Anode : [SbCl6 ]3  [SbCl6 ]  2e

2Br   Br2  2e

Cathode : 2H   2e  H 2

The reaction occurs when titration of electric quantity:

[SbCl6 ]3  Br2  [SbCl6 ]  2Br  (2)

Applying Faraday's law, we have:

AIt 160  2.4125  103  12  60

mBr2    0.00144(g)
nF 2  96500

From (1) and (2) we have the mass of Sb2O3 in the sample:

0.00144  291.5
mSb2O3   0.00131175(g)
2  160

0.00131175  106
So: ppmSb2O3   87.45 ppm
15

Exercise 6:
Electrolysis of Co2+ 0.100M and Cd2+ 0.0500M solutions.

a. Calculate Co2+ concentration when Cd2+ starts electrolysis.

b. Calculation of cathode potential to reduce Co2+ ion concentration to 1.0  10-6

M.

For Cd2+ to start electrolysis: Cd2+ + 2e Cd

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

Given that: EoCo2 /Co =  0.280V; ECd

o
2
/Cd
=  0.402V

Solution:

a. Calculate Co concentration so that Cd2+ starts electrolysis.

The reactions in the cathode:

Co2+ + 2e Co

Cd2+ + 2e Cd

Let Cd start electrolysis, then the cathode

0.059
Ec =ECd2+ /Cd  ECd
0
2+
/Cd
 log[Cd 2+ ]
2

0.059
 E c   0.402  log 0.0500  0.440V
2

0.059
Then: ECo2+ /Co  Ec =ECo2+ /Co 
0
log[Co2+ ]
2

2(Ec  E0 ) 2(-0.44  0.28)

Co2 /Co
2
 [Co ] = 10 0.059
 10 0.059
 1.94 103 M

So we can not completely separate Co from Cd

b. Calculation of the cathode to reduce Co2+ concentration to 1.0  10-6 M

We have:

0.059
E c  E Co2+ /Co  E Co
0
2+
/Co
 log[Co 2+ ]
2
0.059
 0,280  log106   0.457V
2

So when the cathode potential is -0.457V, the concentration of Co2+ is only 1.0 
10-6 M.

8
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Co2+ is considered completely separated from the electrolyte solution.

Exercise 7:

a) Calculation of cathode potential for complete separation of Cu

from the mixture of CuSO4 0.010M and ZnSO4 0.010M using two
Pt electrodes in 1M H2SO4.

b) When Zn2+ starts electrolysis, what is the concentration of Cu2+

remaining?

Solution:

Possible processes:

At the cathode :

Cu2+ + 2e  Cu

0.059 0.059
ECu 2 Cu  ECu
o
2
Cu
 lg[Cu 2 ]=0.34+ lg 0.010  0.28V
2 2
Zn2+ + 2e  Zn

0.059 2 0.059
E Zn2
Zn
 E oZn2 Zn
 lg[ Zn ]=  0.76+ lg 0.010   0.8 2V
2 2
So, at the cathode Cu2+ electrolysis first.

To separate Cu2+ from solution, the concentration of Cu2+ remains

less than 10-6M

0.059 0.059
ECu 2 Cu  ECu
o
2
Cu
 lg[Cu 2 ]=0.34+ lg106  0.16V
2 2
To Cu separated completely, we have : E Zn2 Zn  EC <ECu 2 Cu

So : -0,82V< EC < 0,16V

When Zn2+ starts electrolysis, EC = -0,82V

0.059
ECu 2 Cu  E Cu
o
2
Cu
 lg[Cu 2 ]=  0.82 V
2
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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

 Cu 2  1040 M

Exercise 8:
A 0.3619-g sample of tetrachloropicolinic acid, C6HNO2Cl4, is dissolved in distilled
water, transferred to a 1000-mL volumetric flask, and diluted to volume. An
exhaustive controlled-potential electrolysis of a 10.00-mL portion of this solution at a
spongy silver cathode requires 5.374 C of charge. What is the value of n for this
reduction reaction?

Solution

The 10.00-mL portion of sample contains 3.619 mg, or 1.39 × 10–5 mol of
tetrachloropicolinic acid.

We have

Q 5.374C
n 
F N A  96478C / mol e   (1.39 105 mol C6 HNO 2Cl 4 )
 4.01mol e  / mol C6 HNO 2Cl 4

Thus, reducing a molecule of tetrachloropicolinic acid requires four electrons. The

overall reaction, which results in the selective formation of 3,6-dichloropicolinic acid,
is

Exercise 9:
Suppose that a solution containing 0.20 M Cu2+ and 1.0 M H+ is electrolyzed to
deposit Cu(s) on a Pt cathode and to liberate O2 at a Pt anode. Calculate the voltage
needed for electrolysis. If the resistance of this cell is 0.44 ohm. Estimate the
voltage needed to maintain a current of 2.0 A. Assume that the anode overpotential
is 1.28 V and there is no concentration polarization.

10
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

11
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Solution:

Cathode: Cu 2  2e  Cu(s) E o  0.339V

1
Anode: H 2O O 2  2H   2e  E o  1.229V
2
1
Net reaction: H 2O + Cu 2 Cu(s)  O 2 ( g )  2H  E o  0.890V
2
Assuming that O2 is leberated at a pressure of 0.20 atm, we naively calculate the
voltage needed for the electrolysis as follows:

0.05916 PO1/2 [H  ]2
E E  o
log 2

n [Cu 2 ]
0.05916 (0.20)1/2 (1.0)2
  0.890  log  0.900V
2 (0.20)

In the absence od any polarization effects, we expect that no reaction should occur if
the applied voltage is more positive than -0.900V. When the voltage is more negative
than -0.900V, we expect deposition of Cu and liberation of O2 to occur.

E applied  (E cathode  E anode )  IR  overpotential

 E eq  IR  overpotential
 0.900V  (2.0A)(0.44)  1.28V
 0.900V  0.88V  1.28V  3.04V

Exercise 10:
A solution containing 0.1M Cu2+ and 0.1 M Sn2+ calculate:

The potential at which Cu2+ starts deposition.

The potential ate which Cu2+ is completely deposited (99.99% deposition).

The potential at which Sn2+ starts deposition.

• Would Sn2+ be reduced before the copper is completely deposited?

• From the standard potentials given below we expect that Cu2+ be reduced more
easily than Sn2+

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Solution:

Cu 2  2e Cu(s) E o  0.339V

Sn 2  2e Sn(s) E o  0.141V

The cathode potential at which Cu2+ ought to be reduced is calculated as

0.059 1
E  0.337  log  0.189V
2 1.00 105
Ecell =  0.156  0.244=  0.400V

If 99.99% of the Cu2+ were deposited, the concentration of Cu2+ remaining in solution
would be 10-5 M, and the cathode potetial required to continue reduction would be

0.05916 1
Ecathode  0.339  log 5  0.19V
2 10

At a cathode potential of 0.19 V, then, rather complete deposition of copper is

expected. Would Sn2+ be reduced at this potential? To deposit Sn(s) from a solution
containing 0.1 M Sn2+, a cathode potential of -0.17 V is required:

For reduction of Sn 2
0.05916 1
E (cathode)   0.141  log
2 [Sn 2 ]
0.05916 1
 0.141  log  0.17V
2 0.1

We do not expect significant reduction of Sn2+ at a cathode protential more.

Exercise 11:
Calculate the time required when electrolyte solution Co (II) is precipitated

a. 0.500 gram Co metal on cathode

b. 0.602 grams of Co3O4 on anode

Knowing the electrolytic intensity is 1.00A; E0Co2+ /Co  0,280V

Solution:

a. Calculate the electrolytic time to precipitate 0.500 grams of Co metal into the
cathode
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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Electrodes reaction in cathode: Co2+ + 2e Co

Applying the law of Faraday we have:

AIt nFm 2  96500  5.00

m t   16355.93s  4.54h
nF AI 59  1

Thus, to precipitate 0.500 grams of Co, electrolysis must be carried out with the
current intensity of 1A in a time of 4.54 hours.

b. Calculate the electrolysis time to precipitate 0.602 grams of Co3O4 onto the
cathode

At the cathode: 3Co2+ + 4H2O + 6e Co3O4 + 4H2

nFm 6  96500  0.602

t   14463s  4h
AI 2411

Thus, to precipitate 0.602g Co3O4, it is required to conduct electrolysis with current

intensity 1A for 4 hours.

Exercise 12:
Is a quantitative separation of Cu2+ and Pb2+ by electrolytic deposition feasible in
principle? If so, what range of cathode potential (vs. SCE) can be used? Assume that
solution is initially 0.1000 M in each ion and that quantitative removal of an ion is
realized when only 1 part in 10,000 remains underposited.

In Appendix 5, we find

Cu 2  2e Cu(s) E o  0.337V

Pb2  2e Pb(s) E o  0.126V

Solution

It is apparent that copper will begin to deposit before lead because the electrode
potential for Cu2+ is large than that for Pb2+. Let us first calculate the cathode potential
required to reduced the Cu2+ concentration to 10-4 of its original concentration ( that is,
to 1.00×10-5 M). Substituting into the Nernst equation, we obtian

14
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
0.059 1
E  0.337  log  0.189V
2 1.00 105

Similarly, we can derive the cathode potential at which lead begins to deposit:

0.059 1
E   0.126  log  0.156V
2 0.100

Therefore, if the cathode potential is maintained between 0.189 V and -0.156 V (vs.
SHE), a quantitative separation should in theory occur. To convert these potentials to
potentials relative to a staturated calomel electrode, we treat the reference electrode as
the anode and write

Ecell = Ecathode  ESCE  0.189  0.244=  0.055V

and

Ecell =  0.156  0.244=  0.400V

Therefore, the cathode potential should be kept between -0.055 V and -0.400V versus
the SCE.

Exercise 13:
Conduct electrolysis of 100 ml of a mixture of Cu(NO3)2 0.15 M and 0.1 M AgNO3
(inert electrode) with a current of 1A. Calculate the mass of substances obtained in
anode and cathode when the electrolysis time is:

a) 16 minutes 5 seconds;

b) 32 minutes 10 seconds;

c) 64 minutes 20 seconds.

Solution:

According to the article we have:

Electrode reactions:

At the cathode: Ag  + e → Ag

Cu 2 + 2e → Cu

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
At the anode: 2H2O O2 + 4H+ + 4e

The electrolysis time of Ag  is:

AIt nFm F 96500

m t  n Ag   0.01  965s  16m5s
nF AI I 1
2
Time to Cu electrolysis:

2F 2  96500
t  n Cu2   0.015   2895s  48m15s
I 1
Thus, after 16 minutes 5 seconds + 48 minutes 15 seconds = 64 minutes 20 seconds,
2
both Cu and Ag  are electrolyzed.

a) After 16 minutes 5 seconds

2
At the cathode: Cu has not been electrolyzed; Ag  electrolysis

At that time:

n Ag  n Ag  0.01mol  mAg  0.01108  1.08g

At the anode:

AIt 32  1 (16.60  5)
m O2    0.08g
nF 4  96500

b) After 32 minutes 10 seconds:

At the cathode: Ag  has been electrolyzed:

 mAg  1.08g

2
Electrolytic time Cu is: t = 32 minutes10 seconds - 16 minutes 5seconds =
16minutes 5 seconds

AIt 64  1 (16  60  5)
mCu    0.32g
nF 2  96500

At the anode:
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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

AIt 32  1 (32.60  5)
m O2    0.16g
nF 4  96500

c) After 64 minutes 20 seconds:

2
At the cathode: Ag  and Cu are all electrolyzed

 mAg  1.08g

n Cu  n Cu2  0.015mol  mCu  0.015  64  0.96g

At the anode:

AIt 32  1 (34.60  5)
m O2    0.32g
nF 4  96500

Exercise 14:
Electrolyte of NiSO4 0.100M solution with pH = 2.00 using Pt electrode.

a. The cathode potentiality needed to have Ni precipitate in the cathode

b. Calculate the voltage needed to have the first electrolysis process

c. Calculating the voltage that must be applied to [Ni2+] is equal to

1.0  10-4 M.

Electrolytic flask resistance: R = 3.15; I = 1.10A

Solution:

a. At cathode: Ni2+ +2e Ni

To have Ni precipitate in cathode, the cathode Ec  E Ni2 / Ni

Which

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

0.059
E Ni2 / Ni  E 0 2  log  Ni 2 
Ni / Ni 2
0.059
 0.230  log101  0.2595V
2

So to have the precipitate Ni appear in the cathode, the cathode potential :

E c  -0.2595V

b. The proces at electrode :

At the cathode:

Ni 2  2e Ni 1 E Ni2 / Ni

2H   2e H2   2 E 2H /H
2

E 2H /H  E 02H  /H  0,059log[H  ]

2 2

 0.00  0.059log102  0,118V  E Ni2 / Ni

When the electrolysis starts the process (2) takes place.

At the anode:

2H2O O2  4H   4e

EO2 /H2O = EO0 2 /H2O + 0.059 .log[H+ ]  1.23  0.059log102  1.112V

The minimum voltage to put in for the electrolytic process to start happening is:

V  (E a  a ) – (E c  c )  IR

 V  1.112  0.80  –  – 0.118  0.00   1.10  3.15  5.495V

So when putting in a minimum voltage of 5.495V, the electrolysis process starts

to happen.

c. In order for [Ni2+] to be 1.0  10-4 M then the cathode potential:

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

0.059
E c  E Ni2 / Ni  E 0 2  log  Ni 2 
Ni / Ni 2
0.059
 0.230  log104  0.348V
2

Then the voltage to be applied is:

V  (E a  a ) – (E c  c )  IR

 V  1.112  0.80  –  – 0.348  0.00   1.10  3.15  5.725V

So, we have to put a voltage equal to 5.725V so that the concentration of Ni2+
remaining after electrolysis is 1.0  10-4 M.

Exercise 15:
To quantify H2S in water, 100.0 ml of water is taken into the electrolysis flask, with
extra KI. Here I  is oxidized in anode, I3 produces oxidation of H2S. The
electrolytic end point is determined based on the blue formation of iodine - starch
paste. Calculate the number of ppm H2S in the water if the electrolyte with a
constant current intensity is 36.12mA for 10 minutes 25 seconds.

Solution:

Reactions at anode electrode:

3I I3  2e (1)

I3  S2 S  3I (2)

2
When the S ends then I3 I  I2 . I 2 will produce green starch.

Applying Faraday's formula we have:

m I 1 It 1 36.12  103  (10  60  25)

n I  3
     1.17  104 mol
3
A I F n 96500 2
3

4
According to (2) : n H 2S  n I  1.17  10 mol
3

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

m H2S  1.17  104  34  4  103 g  4  103 g

4  103  106
 (ppm)H2S   40 ppm
100

So the content of H2S in water is 40ppm.

Exercise 16:
The concentration of H2S in the drainage from an abandoned mine can be determined
by a coulometric titration using KI as a mediator and I3– as the titrant.

H2S(aq)  I3 (aq)  2H2O(l ) Ç 2H3O (aq)  3I  (aq)  S( s)

A 50.00-mL sample of water is placed in a coulometric cell, along with an excess of
KI and a small amount of starch as an indicator. Electrolysis is carried out at a constant
current of 84.6 mA, requiring 386 s to reach the starch end point. Report the
concentration of H2S in the sample in parts-per-million.
Solution:

H2S(aq)  I3 (aq)  2H2O(l ) Ç 2H3O (aq)  3I  (aq)  S( s)

Reactions at anode electrode:

3I I3  2e (1)

I3  S2 S  3I (2)

2
When the S ends then I3 I  I2 . I 2 will produce green starch.

Applying Faraday's formula we have:

m I 1 It 1 84.2  103  386

n I  3
     1.168  104 mol
3
A I F n 96500 2
3

4
According to (2) : n H2S  n I  1.168  10 mol
3

m H2S  1.168  104  34  5.72  103 g  5.72 103 g

5.72  103  106
 (ppm) H2S   114.48 ppm
50

So the content of H2S in water is 114.48 ppm.

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Exercise 17;
Add 0.5A of electric current through the salt solution of an organic acid for 2 hours.
The result after the electrolysis process is on the cathode producing m grams of a
metal and on the anode the ethane gas and carbon dioxide escape. (Knowing that
there is no gas escaping from the cathode)

a. Which salt of metal is electrolytic? What is the value of m? Know that 5.18 grams
of that metal pushes 1.59 grams of Cu from copper sulfate solution.

b. Which salt of organic acid is electrolytic? Write down the reaction equations that
occur on the electrodes.

Solution:

a. The reaction equation occurs when immersing the metal rod into CuSO4 solution:

2M  nCu 2  2M n   nCu
2 2 1.59 0.05
n M =  n Cu    (mol)
n n 63.5 n
5.18
M  n  103.6  n
0.05

n 1 2 3

M 103.6 207.2 310.8

(not choose) (Pb) (not choose)

So the salt given is salt of Pb2 +.

1 A 1 207
Apply Faraday formula: m    It    0.5  2  3.86g
F n 26.8 2

b. Electrolytic organic salts of carbon dioxide and Pb:

The salt is (CH3 – CH2 – COO)2Pb (Lead propionate)

Electrolysis process:

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

At the cathode: Pb2  2e Pb

At the anode:

()
CH3  CH 2  COO CH3  CH 2  CO2  2e
()
CH3 CH 2  H 2O CH3  CH3  OH 
2H 2O 4H   O2   4e

Exercise 18:
Consider the 1M ZnSO4 electrolysis process when:

a. Performed in 1N H2SO4 medium.

b. Perform in acetate buffer with pH = 6, if electrolytic use of cathode plating Cu and

current density when electrolysis is 0.01 A/cm3=.

Solution:

When electrolysis of 1M ZnSO4 solution may have electrolytic processes that occur as
follows:

Cathode: Zn 2  2e Zn(s) E cb  0.76 V

2H   2e H2 E cb  0.00 V
Anode: H 2O  4e 4H   O2 E cb  1.23V

a. The overpotential of hydrogen on the Cu catot when the flow density is 0.01
A/cm3= = is -0.584V. So: E '2H+ /H  0.584V
2

Which E'Zn2+ /Zn  0.76V should be in the cathode will have H2 gas escaping

without Zn separating.

In a buffer solution with pH = 6, the equilibrium potential for the hydrogen electrode is
Ecb  0.00  0.059log106  0.345V

Then E'c  0.584  0.345  0.938V < EoZn2+ /Zn  0.76V

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Zn cathode should be separated in advance.
In fact, at E c  0.938V , the concentration of the remaining Zn2+ is calculated
by the following equation:
0.059
0.938  0.76  log[Zn 2+ ]
2
7
 [Zn ]  10 V
2+

Thus, Zn can be considered completely separated under this pH condition.

Exercise 19:
A sample of brass containing Cu and Pb. Dissolving 1,581 grams of sample in acid
and conducting electrolysis under appropriate conditions yielded 1,003 grams of Cu
in catot and 0.0750 grams of PbO2 in anode. Write down the electrolytic reaction
equations.
Calculate the content of% Cu and Pb in the sample.

Solution:

Electrolysis process:

At the cathode : Cu 2  2e Cu
2H   2e H2 
Pb 2  O 2  2e PbO 2
At the anode : 2H 2O 4H   O 2   4e

According to the law of conservation of element, we have:

mCu in the sample  mCu after electrolysis  1.003g

1.003
%Cu   63.44%
1.581

0.0750
mPb in the sample = mPb after electrolysis =  207  0.0650 g
239

0.0650
%Pb   4.11%
1.581
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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
Thus, the %w/w copper and lead in the sample of bass are:

%Cu  63.44%
%Pb  4.11%

Exercise 20:
Electrolysis of NaCl solution using cathode electrode is a Hg flow of amalgam and
using titanium (Ti) ruthenium (Ru) and rodium (Rd) poles as anode. The distance
between the cathode and anot is about a few millimeters

a) Write down the reaction equations that occur at the electrodes at the beginning of
electrolysis (pH = 7). Credits of electrode potential values and resolution potentials.

b) After a while the pH goes up 11. Explain why? Write the reaction equation at that
pH? Calculating electrode potential and resolution potential

For : E Na  / Na  2.71V; E 2H + /H 2  0.00V; E O2 /H 2O  1.23V;

0 o o

E Na + / Na (Hg)  1.78V with NaCl 25% and 0.2% Na

E Cl   1.34V with NaCl 25%
2 /2 Cl

H2 (Hg)  1.3V; O2 (Ru/Rd)  0.8V

Solution:

a). In NaCl solution

NaCl  Na   Cl
H2O H  OH

When electrolysis:

At the cathode:

Na  + Hg + e Na(Hg) (1)
H 2O H   OH  | 2
H  2 e H2
2H 2O  2 e H 2  2OH  (2)

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
At the anode:

2H2O O2  4H  4e (3)

2Cl Cl2  2e (4)

E Na + / Na (Hg)  1.78V
E 2H+ /H  0.00  0.059log107  0.413V
2

E '2H+ /H  E2H+ /H  H2  0.413  1.3  1.713V

2 2

 E '2H+ /H ( 1.731V)  E Na + / Na (Hg) ( 1.78V)  E 0Na + / Na ( 2.71V)

2

so when the electrolysis starts at the cathode the process will be the process (2),
with H2 released at the cathode.

At the anode:

From (3) we have:

E O2 /H2O = E 0O2 /H2O + 0.059 log[H + ]  1.23  0.059log107  0.817 V

E 'O2 /H2O = E O2 /H2O + O2  0.817  0.80  1.617 V

We have: E Cl  ( 1.34V)  E 'O2 /H2O ( 1.671V) so in the anode, the process

2 /2Cl

(4) occurs, with Cl2 escaping.

So the electrolytic reaction happens

At the cathode : 2H 2 O  2e H 2  2OH 

At the anode : 2Cl Cl 2  2e
2Cl  2H 2O H 2  Cl 2  2OH 

Resolution: V  E a  Ec  1.34  1.713  3.053V

' '

b) After electrolysis time, the concentration of OH- increases so the pH increases,

reaching 11.

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam
At pH = 11, the electrolyte reaction occurs:

At the cathode: pH = 11, = 10-11 M

0.059
Ec  0.938V  0.76  log[Zn 2+ ]
2
 [ZEn 2+ ]  107 V

Therefore, in the cathode there is a process (1) occurring:

Na   Hg  e Na  Hg 

At the anode:

E O2 /H2O = E O0 2 /H2O + 0.059 log[H + ]  1.23  0.059log1011  0.581V

E 'O2 /H2O = E O2 /H2O + O2  0.581  0.80  1.381V

We have: E Cl  ( 1,34V)  E 'O2 /H2O (  1,381V) so Cl2 still exits:

2 /2Cl

Electrolysis process:

At the cathode : Na   Hg + e Na(Hg) | 2

At the anode : 2Cl Cl 2  2e
2Na  + 2Cl   2Hg Cl 2  2Na(Hg)

Resolution:

V  E'a  E'c  1.34  1.78  3.12V

26
Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

PART 3: CONCLUSIONS

Coulometric methods are based on oxidation or reduction of an electrolyte

analyzer for a long enough time to quantify the analyte quantitatively to the new
oxidation state.

The practice of solving coulometry exercises:

- Help students and students improve their knowledge, expand the scope of
research on advanced exercises, intensive in analytical chemistry.

- Learn, absorb the progress of countries, develop analytical chemistry in our

country.

- Know the good exercises, good solutions, new, to serve the fostering team of
excellent students and students.

Through the essay, it helps students and students to learn more deeply and
improve the ability to solve exercises on coulometric methods, thereby improving their
learning and knowledge.

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Lecturer: Assoc. Prof. Ngo Van Tu Student: Nguyen Thi Thanh Tam

REFERENCE MATERIALS

[1] David Harvey (2000), Modern analytical chemistry, McGraw- Hill Higher
Education

[2] PGS.TS. Nguyễn Đình Luyện - TS. Ngô Văn Tứ, Giáo trình Phương pháp
phân tích lý hóa, NXB Đại học Huế.

[3] Bassett, J.; Denney, R. C.; Jeffery, G. H.; Mendham,( 1978),Quantitative

Inorganic Analysis, Longman: London.

[3]https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Book%3A_An
alytical_Chemistry_2.0_(Harvey)/11_Electrochemical_Methods/11.3%3A_Coulometri
c_Methods#Practice_Exercise_11.7

[4] http://web.iyte.edu.tr/~serifeyalcin/lectures/chem306/cn_4.pdf

[5]https://www.academia.edu/37376709/Quantitative_Chemical_Analysis_8th_E
dition_PDF_eTextBook_1_?fbclid=IwAR1kHzxz8H4FGbhB7gl_MCMC-
hCxZnq6YTeJ3pRjIp3oLUfj8nRkA-GTATs

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