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Methods
Dr. Eveliina Repo
Lappeenranta University of Technology
eveliina.repo@lut.fi
What is electrochemistry?
Short definition:
Electrochemistry deals with the charge transfer at
the interface between an electrically conductive
(or semi-conductive) material and an ionic
conductor (e.g. liquids, melts or solid electrolytes) as
well as with the reactions within the electrolytes and
the resulting equilibrium
What is oxidation?
When a molecule/ion loses electrons
(becomes more positive)
Whatever is oxidized is the reducing agent
What is reduction?
When a molecule/ion gains electrons
(becomes more negative)
Whatever is reduced is the oxidizing agent
• E0 is for the reaction as written
• The more positive E0 the greater the
tendency for the substance to be
reduced
• The half-cell reactions are reversible
• The sign of E0 changes when the
reaction is reversed
• Changing the stoichiometric
coefficients of a half-cell reaction
does not change the value of E0
http://highered.mheducation.com/olcweb/cgi/pluginpop.cgi?it=jpg::::::/sites/dl/free/00236546
66/650262/Standard_Reduction_Potential_19_01.jpg::Standard%20reduction%20potentials
Cell potential
Cell potential:
E0cell = E0Zn Zn2+ + E0Cu2+ Cu = +0,76 V + 0,34 V = 1,1 V Positive: spontaneous
nFE nFE RT ln Q
RT T = 25 oC 0.0591
E E ln Q E E ln Q
nF n
C D
A B C D Q
A B
Example: Electrochemical cell
2
0.0591 Al 3 0.0591 1.502
E E ln 3
0.48 ln 0.47V
n Mn 2 6 0.503
Electrochemical water/soil treatment
Benefits of electrochemical Methods:
technologies: Electrochemical oxidation
Environmental compatibility Electrocoagulation
Versatility Electrochemical reduction
Energy efficiency Indirect electro-oxidation with
Safety strong oxidants
Selectivity Electrodeionization
Fe – 2e- Fe2+
Fe2+ + 2OH- Fe(OH)2 (at alkaline conditions)
Just published:
Hakizimana, J. N., Gourich, B., Chafi, M., Stiriba, Y., Vial, C., Drogui, P., & Naja, J.
(2017). Electrocoagulation process in water treatment: A review of
electrocoagulation modeling approaches. Desalination, 404, 1-21.
Municipal wastewater treatment
EC unit EC unit
Chemical for Chemical for
phosphorous phosphorous
precipitation CaO precipitation (Polymer)
Sand separation
Incoming
wastewater
Circulated sludge
(Polymer)
Excess sludge
http://www.waterworld.com/articles/iww/print/volume-13/issue-5/features/embracing-closed-loop-technology-for-recycling-
and-reuse.html
https://www.wateronline.com/doc/a-shocking-approach-to-wastewater-treatment-0001
Treatment of the process water in oil re-
refining industry
Enhance organics
removal by EC
Rain water Sulfuric
Precipitation
COD: 11000 mg/L tank acid H2O2 chemical Lime
Stripped
Process Aeration Residence Coagulation
process
water feed tank tank tank
water
Polymer
To municipal
water treatment
plant
Electroflotation
Tiny oxygen and hydrogen bubbles are formed at anode and
cathode, respectively, during water electrolysis
Bubbles attach to suspended matter float to the surface (DAF)
Graphite, titania or dimensionally stable anode (DSA) electrodes
http://envirochemie.com/en/plants/flotation-
plants/electroflotation/
Electroflotation
Factors affecting
1) Size of the bubbles
2) Cell design and arrangement of the electrodes
3) Electrode materials
4) Operating conditions, such us current density and water conductivity
5) pH
Applications
1) Separation of oil and low-density suspended solids from wastewaters
2) Used e.g. in mining, dairy and restaurant wastewater treatment
Electrochemical oxidation (EO)
Indirect EO processes
Chlorine and hypochlorite generated anodically
Electrochemically generated hydrogen peroxide
Mediated EO where metal ions are oxidized on an anode to form high valence
reactive species, which attack pollutants or generate hydroxyl radicals
Oxygen
Formation potentials of different oxidants
2 H + + 2 e- H2 E0 = 0.0
2 H2O O2 + 4 e- + 4 H+ E0 = + 1.23
2 Cl- Cl2 + 2e- E0 = + 1.36
Cl- + H2O HOCl + 2 e- + H+ E0 = + 1.49
3 H2O O3 + 6 e- + 6 H+ E0 = + 1.51
2 H2O H2O2 + 2 e- + 2 H+ E0 = + 1.77
O2 + H2O O3 + 2 e- + 2 H+ E0 = + 2.07
H2O OH• + e- + H+ E0 = + 2.85
Reactions:
Sonoelectro-Fenton
Ultrasound accelerates the regeneration of ferrous ions and
enhances the radical formation further
Examples
Babuponnusami, A., & Muthukumar, K. (2012). Advanced oxidation of phenol: a comparison between Fenton, electro-Fenton, sono-electro-
Fenton and photo-electro-Fenton processes. Chemical Engineering Journal, 183, 1-9.
Sonoelectrocatalysis
Ultrasound treatment is
Bulk solution OH• (aq) + P(aq) products H2O2 + P(aq) products
T ~ 300 K
https://commons.wikimedia.org/wiki/File:Electrodialysis.jpg, cc-license
Electrodialysis
Advantages Disadvantages
Deionization occurs
by applying a
+ + + - -------- voltage over two
- - -
V -+
+-
porous carbon
electrodes
+ + -+ + +
- ++++ ++++ Desalinated water
+
Desalination comparison
https://www.youtube.com/watch?v=PstkfJoIBUU
Our CDI system for REEs recovery
00.0 V
Potentiostat : : :
CDI cell
Conductivity
Current on Current off
Peristaltic pump
PC plate
Spacer Electrode
Collector
PC plate
Electrodeionization
Arar, Ö., Yüksel, Ü., Kabay, N., & Yüksel, M. (2014). Various applications of
electrodeionization (EDI) method for water treatment—A short review.
Desalination, 342, 16-22.
Case: Electrocoagulation in pulp
and paper mill water treatment
Aim to investigate if electrocoagulation can be used for coagulation
in paper mill raw water purification and if there are beneficial effects
in the combination of chemical and electrochemical coagulation
Methodology
Paper mill mechanically treated water was used in the experiments.
Before treatment salt, chemical coagulant and pH adjustment chemical
were added.
Water was stirred in the flocculator after EC treatment and samples were
pipetted, filtered or flotated with DAF (dissolved air flotation).
2
Date Series PAC (mg/l) NaOH (mg/l) Current density (mA/cm
NaCl (mg/l) )
DAF Filtered Pipetted
50
40
30
20
10
0 20 40 60 80 100 120 140 160
Electric charge (C)
24
KMnO4 (mg/l)
23
22
21
20
Schematic diagram showing different positions and conditions of electrodes (A: a reference
column, B: anode at the surface of the sediment, C: anode 4 cm below the surface of the
sediment used for various voltages, D: cathode at the surface of the sediment)
Initial Equilibrium stage After 415 days
Col-1 RC
Col-2
Col-2 Col-1
RC
A
C
Cr [µg/L]
Cr [µg/L]
pH
60
-
6 10
pH
150 50
-
a 40 b 9
4
+
100 8
30
+
20 7
50 2
10 6
0 0 0 5
0 4 10 36 39 48 67 76 91 105 121 136 151 169 181 0 4 10 36 39 48 67 76 91 105 121 136 151 169 181
Time (days) Time (days)
U= 0V (I) 10
140 U= 3V (II) U= 0V(III) 100 U= 0V (I) U= 3V (II) U= 0V(III) 14
9
90 13
120 8
80 12
7
100 70
Cr [µg/L]
11
6
Cr [µg/L]
60
pH
80 10
pH
5 50 d
60 c 4 40
9
3 8
30
40
+ -
2 20 7
20 10 6
1
- 0
0 4 10 36 39 48 67 76 91
0
105 121 136 151 169 181
0
0 4 10 36 39 48 67 76 91
5
105 121 136 151 169 181 +
Time (days)
Time (days) Conc. (Reference Column) Conc. (Experimental Column)
pH (Reference Column) pH (Experimental Column)
Powe r supply
Cathode
- Sludge
Sand bed
Gravel bed
Dewater
50
By anode
Solid Content (%)
40
Sludge cake
30 By cathode
20
10
0
Blank 3V 5V 10V 15V 20V 30V
200
5V
Dewatering rate (l/m2.d)
10V
150 15V
20V
100 30V
50
0
0 1 2 3 4
Tim e (d)
8 Anaerobic 16
R e m o v e w a t e r r a t e ( l/ m 2 )
Anaerobic
7 14
6 12
5 10
4 8
3 6
2 4
1 2
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Time (h) Time (h)
The water remove rate as function of time at the anode and the cathode
during pressure electro dewatering using different types of sludge
Conclusions