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Figure 2.1
voltaic cell
Balance by
redox reaction
Half reaction method Oxidation number method
electrolytic cell
GER!
Molecular reaction
E.g. : KMnO4 + H2C2O4 + H2SO4 K2SO4 + MnSO4 + CO2 + H2O
7 2. Balance the total atom in elements undergoing oxidation and reduction by giving coefficient of reaction KMnO4 + H2C2O4 + H2SO4 K2SO4 + MnSO4 + 2 CO2 + H2O 3. Determine the total change of oxidation number for each oxidation and reduction reaction and balance the total change of oxidation number by fixed coefficient
+7 5e x 2 +2
2e x 5
2(+4) = +8
8 4. Balance the other elements from metal, non-metal, H and O 2 KMnO4 + 5 H2C2O4 + 3 H2SO4 K2SO4 + 2 MnSO4 + 10 CO2 + 8 H2O Elements K S H Left 2 1 16 Right 2 3 2
5. Redox reaction will be balance if the total of O on left equals with the total of O on right
Ionic reaction
E.g. : MnO4- + C2O42- Mn2+ + CO2 ( in acidic solution )
1. Determine whether it is oxidation and reduction reaction based on the elements undergoing oxidation number change
+7
2. Balance the total atom in elements undergoing oxidation and reduction by giving coefficient of reaction MnO4- + C2O42- Mn2+ + 2 CO2
3. Determine the total change of oxidation number for each oxidation and reduction reaction and balance the total change of oxidation number by fixed coefficient
5e x 2 +7 +2
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2 MnO4- + 5 C2O42- 2 Mn2+ + 10 CO2 4. Balance the charge on the left side and on the right side in the redox reaction by : Adding H+ if in acidic solution Adding OH- if in alkaline solution
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Practice Exercise Balance the following redox reaction by oxidation number method
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1. Divide the reaction into half-reactions, one for oxidation and the other for reduction. Cr2O72- Cr3+ Cl- Cl2 ( reduction )
( oxidation )
Cr2O72- 2 Cr3+
2 Cl- Cl2 3. If in acidic solution, so add H2O on O-deficient side and add H+ on other side for H-balance. If in alkaline solution, so add H2O on O-over side and add OH- on other side for H-balance Cr2O72- + 14 H+ 2 Cr3+ + 7 H2O 2 Cl- Cl2
4. Balance the charge of each reaction by adding electrons Cr2O72- + 14 H+ + 6 e 2 Cr3+ + 7 H2O 2 Cl- Cl2 + 2 e
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Practice Exercise
Balance the following redox reaction by ion-electron method
1.
2. 3. 4.
5.
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Practice Exercise
Balance the following redox reaction by ion-electron or oxidation number method 1. 2. 3. 4. 5. Cr2O72- + Fe2+ Cr3+ + Fe3+ (in acidic solution) MnO4- + SO32- MnO42- + SO42- (in alkaline solution) Sn2+ + IO4- Sn4+ + I- (in acidic solution) S2O32- + I2 S4O62- + I- (in alkaline solution) Mn2+ + H2O2 MnO2 + H2O (in alkaline solution)
6.
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OXIDATION-REDUCTION REACTIONS
Direct Redox Reaction Oxidizing and reducing agents in direct contact.
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OXIDATION-REDUCTION REACTIONS
Indirect Redox Reaction
A battery functions by transferring electrons through an external wire from the reducing agent to the oxidizing agent.
Figure 2.4
ELECTROCHEMISTRY
Electrochemistry is field of chemistry that studies about relationship between electric energy and chemical energy or reverse. Electrochemical process occurs in an electrochemical cell Electrochemical Cell components Electrode Anode ( a place of oxidation occurs) Cathode ( a place of reduction occurs) Electrolyte solution Anox
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Cared
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Voltaic Cell
chemical energy electric energy
Electrolytic Cell
electric energy chemical energy
KNAP { Cathode ( - ) , Anode ( + ) } not spontaneous redox reaction has no salt bridge
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(oxidation) (reduction)
Electrons move from Zn to Cu directly. It is an indication that these redox reaction obtains electric current. But the electric current cant be detected (measured).
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Figure 2.5
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Zn Zn2+(aq) Cu2+(aq) Cu
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At figure 2.5, the potential is +1.10 V at 25 C and when [Zn2+] and [Cu2+] = 1.0 M. +1.10 V is difference of potential for Zn/Cu cell or it is called as cell potential
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e
H2 Pt
HCl
0,34 v
e
Cu
Salt bridge
Figure 2.6
CuSO4
H2(g) 2 H+ + 2 e Cu2+ + 2e Cu
(Ox) (Red)
Electrode potential of H2 = 0,00 v, so +0,34 v at the figure 2.6 is standard reduction potential of Cu
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Notes : If standard reduction potential for an electrode = + , so the electrode is easier reduced than electrode of H2 If standard reduction potential for an electrode = so the electrode is more difficult reduced than electrode of H2 ,
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E0 (v)
-3,04 -2,92 -2,90 -2,87 -2,71 -2,37 -1,66 -1,18 -0,83 -0,76 -0,74 -0,44 -0,28 -0,28
Reduction Half-Reaction
Ni2+(aq) + 2e- Ni Sn2+(aq) + 2e- Sn Pb2+(aq) + 2e- Pb 2H+(aq) + 2e H2 Cu2+(aq) + 2e Cu O2(g) + 2H2O(l) + 4e- 4OH-(aq) I2(s) + 2e 2I-(aq) Ag+(aq) + e- Ag Hg2+(aq) + 2e- Hg Br2(l) + 2e- 2Br-(aq) O2(g) + 4H+(aq) + 4e- 2H2O(l) Cl2(g) + 2e- 2Cl-(aq) Au3+(aq) + 3e- Au F2(g) + 2e- 2F-
E0 (v)
-0,23 -0,14 -0,13 0,00 +0,34 +0,40 +0.56 +0,80 +0,85 +1,06 +1,23 +1,36 +1,52 +2,87
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From value of standard reduction potential for several electrodes in the table above, we can write down reactivity series of metal OR voltaic series (deret volta)
0,00 v
Li K Ba Ca Na Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Hg Ag Pt Au
E0 << Strong reducing agent Weak oxidizing agent Be easiest oxidized E0 Weak reducing agent Strong oxidizing agent Be easiest reduced
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Example
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Given 2 electrodes :
Mg2+(aq) + 2e Mg(s) Zn2+(aq) + 2e Zns) E0 = -2,37 v E0 = -0,76 v oxidation / anode reduction / cathode
E0cell
= E0high - E0low
= -0,76 v (-237 v) = +1,61 v
Cell potential can be calculated by : Cathode : Zn2+ + 2e Zn Anode : Mg Mg2+ + 2e E0 = -0,76 V E0 = 2,37 V E0 = +1,61 V
Mg + Zn2+ Mg2+ + Zn
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Li K Ba Ca Na Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Hg Ag Pt Au
Mn
K+ + Na
+ Fe2+
Mn2+ +
Fe
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Example
Predict whether the following reactions will be spontaneous or not ! a. Zn(s) + Mg2+(aq) Zn2+(aq) + Mg(s) b. Mg(s) + Ag+(aq) Mg2+(aq) + Ag(s) c. Zn2+(aq) + Ag(s) Zn(s) + Ag+(aq) Solution a. Zn is oxidized and Mg is reduced E0cell = E0red E0ox = -2,37 (-0,76) = - 1,61 b. Mg is oxidized and Ag is reduced E0cell = E0red E0ox = +0,80 (-2,37) = + 3,17 v c. Ag is oxidized and Zn is reduced E0cell = E0red E0ox = -0,76 (+0,80) = - 1,56 v
not spontaneous not spontaneous
spontaneous
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From the arrangement can be concluded : 1. Mg + Zn2+ Mg2+ + Zn 2. Zn + Mg2+ 3. Ag+ + Mg Ag + Mg2+ 4. Zn2+ + Ag
Ni2+ + 2e Ni Ag+ + e Ag
E0 = -0,23 v E0 = +0,80 v
From the electrode potential above : a. Draw the voltaic cell ! b. Write down the reduction reaction ! c. Write down the oxidation reaction ! d. Write down the redox reaction ! e. Write down the cell diagram ! f. Calculate E0cell !
2. Predict whether the following reaction will be spontaneous or not ! a. Sn2+ + Mn Sn + Mn2+ d. Fe + Cu2+ Fe2+ + Cu b. Ni2+ + 2Ag Ni + 2Ag+ e. Al + 3Pb2+ 2Al3+ + Pb
B'wina 36
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a. Choose pair of 2 half-cells which has the highest E0cell and the lowest E0cell b. Write down cell diagram of the reaction
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Fuel Cell
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A (-) : Zn(s)
Zn2+(aq) + 2e-
Figure 2.10
Alkaline Battery
Nearly same reactions as in common dry cell, but under basic conditions (e.g. KOH) Anode (Zn)
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Cathode (MnO2)
Figure 2.11
Overall Reaction :
Mercury Battery
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Figure 2.12
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Anode
Cathode
Figure 2.13
Overall Reaction :
Accumulator
Usage
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Cathode (PbO2)
H2SO4
The reaction in accumulator at time produce electricity : A (-) : Pb(s) + SO42-(aq) C (+) : PbO2(s) + 4H+(aq) + SO42-(aq) + 2eOverall Reaction : PbSO4(s) + 2ePbSO4(s) + 2 H2O(l)
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Accumulator can be recharged by reversing the electron flow if the potential exhausted. Electrons are flowed from cathode to anode. Pb electrode is connected to the negative terminal of the current source
A ( + / PbO2 ) : PbSO4(s) + 2 H2O(l) C ( - / Pb) : PbSO4(s) + 2ePbO2(s) + 4H+(aq) + SO42-(aq) + 2ePb(s) + SO42-(aq)
Overall Reaction :
Ni-Cad Battery
Ni-Cd battery consists of : Cadmium, Cd (anode) Nickel oxide solid (NiO2) (cathode) Electrolyte solution (KOH)
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Anode : Cd(s) + 2 OH- (aq) ---> Cd(OH)2(s) + 2eCathode : NiO2(s) + 2 H2O(l) + 2e- ---> Ni(OH)2(s) + 2 OH-(aq) Overall Reaction :
Figure 2.14
Fuel Cell
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Figure 2.15
Cars can use electricity generated by H2/O2 fuel cells. H2 carried in tanks or generated from hydrocarbons
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Fuel cell consists of a mixture of hydrogen and oxygen, electrode with porous carbon containing platinum metal and alkali solution (KOH) which is between the two electrodes O2 gas is flowed to cathode through electrode H2 gas is flowed to anode
A : 2H2(g) + 4OH-(aq) 4H2O(l) + 4eC : O2(g) + 2H2O(l) + 4e- 4OH-(aq) 2H2(g) + O2(g) 2H2O(l)
Corrosion
Corrosion is electrochemical reaction between a metal and its environment The corrosion of iron, Fe is called rusting. The process of rusting Iron, Fe will rust when both oxygen, O2 and water, H2O are present. Other factors cause rusting of iron are ; acid, electrolyte solution and carbon.
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The rusting of iron, Fe is redox reaction. Oxidation and reduction occur at separate parts of metal surface.
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Fe3+
Fe2+
Anode Fe Fe2+ + 2e e
Cathode
O2 + 2H2O + 4e 4 OH-
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Preventing rusting of iron 1. Iron, Fe are coated on its surface with paint, oil and plastic 2. Coating iron, Fe with other metal through electroplating
Iron, Fe is electroplated by metals which has smaller E0 than E0 of Fe, such as Cr, Zn, Al and Mg
H2O + O2 Layer of Zn Fe Figure 2.17 Coating Fe with Zn Anode Zn (-) : 2 Zn(s) 2 Zn2+(aq) + 4e layer of Zn which flaw
Cathode C (+) : 2H2O(l) + O2(g) + 4e 4OH-(aq) Redox : 2Zn(s) + 2H2O(l) + O2(g) 2Zn(OH)2(s)
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3. Make alloy, such as stainless steel (mixture of Fe, Cr & Ni). Contents of Cr in the alloys is 12 % - 18 %. Cr will be oxidized to form strong and transparency layer is layer of Cr2O3. 4. Give protection of cathode.
This way is used to cover pipelines in earth from corrosion, where metal which more reactive (e.g. Mg) than iron, Fe (based on reactivity series of metal or volta series) is planted in earth and is connected with Fe.
Iron, Fe acts as cathode and magnesium, Mg acts as anode
ELECTROLYTIC CELL
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Inert electrode
Inert electrode
Figure 2.18
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Cathode :
Anode :
Na+ + e Na
2 Cl- Cl2 + 2e
ELECTROLYSIS
Reaction on cathode (Cation is reduced)
1. Ions of IA, IIA, Al+3 , Mn2+ ( aqueous ) 2H2O 2O + 2e 2OH-- + H2 2H+ 2e 2OH + H2 2. Other metal ions Mn+ n+ ne ne M M+ + M 3. H+ ion ( acid ) + ++ 2H+ 2H2e 2e H2 2 H 3. 2. 1.
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22 O2 O2- O2 + 4 e 2
4.
1 , 2 & 3 occurs when use inert electrode (Pt, C, Au) If use non-inert electrode, so the anode will undergo oxidation
M M Mn+ + ne Mn+ + ne
Examples
1. Electrolysis of KI solution by carbon electrode x2 KI (aq) K+ (aq) + I- (aq) Cathode : 2H2O + 2e 2OH- + H2 Anode : 2I I2 + 2e + Reaction : 2KI + 2H2O 2 K+ + 2 OH- + H2 + I2 2KI + 2H2O 2 KOH + H2 + I2
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2. Electrolysis of molten MgCl2 by carbon electrode MgCl2(l) Mg2+(l) + 2 Cl-(l) Cathode : Mg2+ + 2e Mg Anode : 2 Cl- Cl2 + 2e Reaction : MgCl2 Mg + Cl2
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3. Electrolysis of AgNO3 solution by carbon electrode x4 AgNO3 (aq) Ag+ (aq) + NO3- (aq) Cathode : Ag+ + e Ag x4 Anode : 2H2O 4H+ + O2 + 4e + Reaction : 4AgNO3 + 2H2O 4Ag + 4H+ + 4NO3- + O2 4. Electrolysis of NaOH solution by iron electrode NaOH(aq) Na+(aq) + OH-(aq) x3 Cathode : 2H2O + 2e 2OH- + H2 x2 Anode : Fe Fe3+ + 3e Reaction : 6 H2O + 2 Fe 6 OH- + 2 Fe3+ + 3 H2
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5. Electrolysis of molten MgSO4 by carbon electrode MgSO4(l) Mg2+(l) + SO42-(l) Cathode : Mg2+ + 2e Mg Anode : SO42- SO2 + O2 + 2e Reaction : MgSO4 Mg + SO2 + O2
Point to note : Electrolysis of a molten, the cation will be reduced and the anion will be oxidized.
6. Electrolysis of CaBr2 solution by iron cathode and carbon anode + 2+ CaBr2(aq) Ca (aq) + 2 Br (aq) Cathode : 2 H2O + 2 e 2 OH- + H2 Anode : 2 Br Br2 + 2e Reaction : CaBr2 + 2 H2O Ca2+ + 2 OH- + H2 + Br2
Practice Exercise
B'wina
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FARADAYS LAW
Faraday I
The quantity of substance produced on electrode is equal to the quantity of electricity passing through the electrolysis
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m = e F
Ar m xF o.n
Where : m o.n F Q i t = = = = = =
Q it F 96500 96500
mass of substance which produced for electrolysis (gram) oxidation number the total electricity in Faraday the total electricity in Coulomb the total electricity in Ampere time of electrolysis (second)
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Faraday II
If the same quantities of electricity are passed trough several electrolytic cells, substances produced by each cell equals to the equivalent weight
F1 F2 Fn
mn m1 m2 .......... . e1 e2 en
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Examples
1. A molten KCl is electrolyzed using a current of 193 A for 1 minutes. (Ar K = 39 ; Cl = 35,5) a. Write down complete reaction! b. Calculate mass of substance plated on the cathode ! c. Calculate volume of gas which formed on the anode at STP !
Solution
KCl(l) K+(l) + Cl-(l) Cathode : Anode : K+ + e K 2 Cl- Cl2 + 2e x2 x2
b.
1st way
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2nd way
mAg eAg
mCu eCu
m Cu = 15.9 g
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Practice Exercise
1. How many minutes will it take an electric current of 5 A to precipitate all the copper from 500 mL of 0,250 M CuSO4(aq) ? (Ar Cu = 63,5) 2. A current of 0,5 F is passed through 250 L of NaI solution with inert electrodes. When volume of the solution is assumed constant, a. write down complete reaction! b. calculate the volume of gas which produced on cathode at STP? c. what is pH of the solution after electrolysis? 3. Electrolysis cells with inert electrodes were arranged in series. The cells contained solution of CuSO4, AgNO3 and AlCl3. 21,6 g of silver in cell 2 was formed for electrolysis. Calculate a. How many gram of copper was plated out in cell 1? b. What is the volume of Cl2 was produced in cell 3 at RTP? 4. An electrolysis of MSO4 solution produced 0,28 g of M on the cathode. The product of electrolysis can be neutralized by 50 mL of 0,2 M NaOH solution. What is the relative atomic mass of M ?
Electrolysis in Industries
1. Extraction of metals
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There are many industrial applications of electrolysis. The most common application include : Reactive metals such as aluminium and magnesium can be extracted from their ores by electrolysis. In this process, molten compound, concentrated solutions of salts or hydroxide solutions are electrolyzed. 2. Purification of metals Pure copper and silver can be obtained through the process electrolysis.
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3.
Electroplating of metals In electroplating of metals, electrolysis is used to coat one metal onto another metal.