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Faculty-Wide Courses 2009-2010

ELECTROCHEMISTRY

SHEET 3
1- Consider a galvanic cell based on the reaction
Al+++ (aq) + Mg(s) → Al(s) + Mg++(aq)
E Al    → Al  -1.66 v

EMg 
→Mg
 -2.37 v

Give the balanced cell reaction and calculate E° for the cell.

Since a galvanic cell, so that E° have to be +ve value


1-Half reactions
A-Oxidation Mg++ (aq) + 2 e- → Mg(s) 
EMg 
→Mg
 -2.37 v

Mg(s) → Mg++ (aq) + 2 e- 


EMg →Mg 
 2.37 v

B-Reduction Al+++ (aq) + 3 e- → Al(s) E Al  → Al  -1.66 v

2-Balance the equation


3Mg(s) → 3Mg++ (aq) + 6 e- 
EMg →Mg 
 2.37 v

2Al+++ (aq) + 6 e- → 2Al(s) E Al  → Al  -1.66 v

3-Net equation 3Mg(s) +2Al+++ (aq) →3Mg++ (aq)+ 2Al(s)

4- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (-1.66) – (-2.37) = 0.71 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (-1.66) + (2.37) = 0.71 v

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ELECTROCHEMISTRY

2- Describe completely the following galvanic cell based on the following


half reactions.
Cl2 + 2e- → 2 Cl- E°=1.36 v
Br2 + 2e- → 2 Br- E°= 1.09 v

Since a galvanic cell, so that E° have to be +ve value


Note:
As he didn’t give me the final “net” reaction so, I will make assumption which of
the two reaction is will be oxidation “Anode” and which will be reduction “Cathode”,
on my assumption, I will take care that the net value of the E° have to be +ve value
I will assume that the reaction have a E° highest value is the reduction
“Cathode”, and the other is the oxidation “anode” to ensure that the net value of E° is
+ ve value.

1-Half reactions
A-Oxidation Br2 + 2e- → 2 Br- E°= 1.09 v
2 Br- → Br2 + 2e- E°= -1.09 v
B-Reduction Cl2+ 2 e- → 2 Cl - E°= 1.36 v
2-Balance the equation
2 Br- → Br2 + 2e- E°= -1.09 v
Cl2+ 2 e- → 2 Cl - E°=1.36 v

3-Net equation 2 Br + Cl2 → Br2 + 2 Cl -

4- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (1.36) – (1.09) = 0.27 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (1.36) + (-1.09) = 0.27 v

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3- Predict whether the following reaction would proceed spontaneously as


written at 298 K.
Co(s) + Fe++ (aq) → Co++ (aq) + Fe(s)
Given that [Co++] =0.15 M and [Fe++] =0.68 M
E = -0.28 v
C o++ → C o

E = -0.44 v
F e++ → F e

1-Half reactions and balance the equation


A-Oxidation Co++ (aq) + 2e- → Co(s) E°= -0.28 v
Co(s) → Co++ (aq) + 2e- E°= 0.28 v
B-Reduction Fe++ (aq) + 2 e- → Fe(s) E°= -0.44 v

2-Net equation Co(s) + Fe++ (aq) → Co++ (aq) + Fe(s)

3- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (-0.44) – (-0.28) = -0.16 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (-0.44) + (0.28) = -0.16 v
Dependence of Cell Potential on Concentration
4- Nernest Equation
0.0591
E = E - log( Q)
n
E = -0.16 – (0.0591/ 2) * ( log ( [Co++] / [Fe++] )
E = -0.16 – (0.02955) * ( log ( [0.15] / [0.68] )
E = -0.16 – (0.02955) * ( log ( [0.220588] )
E = -0.16 – (0.02955) * ( -0.65641 )
E = -0.16 – (-0.019397 )
E = -0.140 v
Since the value of E is –ve, so that this is an electrolytic cell
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4- Calculate the EMF for the cell based on the following half reactions
VO2 + 2 H+ + e- → VO++ + H2O E° = 1.00 v
Zn++ + 2 e- → Zn E° = -0.76 v
Where: T=25°C [VO2++] =2.0M
[H+]=0.5M
[VO++] =1.0x10-2M
[Zn++]=1.0x10-1M

See page 839, and 840 in CHEMISTRY ZUMDAHL|ZUMDAHL BOOK


EXAMPLE 18.9

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5- Consider the cell described below:


Zn|Zn++ (1.00M) || Cu++ (1.00 M) |Cu
Calculate the cell potential after the reaction has operated long enough for
the [Zn++] to have changed by 0.2 mol/L. (Assume T=25°C)

1-Half reactions and make the Balance


A-Oxidation Zn++ + 2e- → Zn E°= -0.76 v
Zn → Zn++ + 2e- E°= 0.76 v
B-Reduction Cu+++ 2 e- → Cu E°= 0.34 v

2-Net equation Zn + Cu++ → Cu + Zn++

3- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (0.34) – (-0.76) = 1.1 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (0.34) + (0.76) = 1.1 v

Dependence of Cell Potential on Concentration


4- Nernest Equation
0.0591
E = E - log( Q)
n
E = 1.1 – (0.0591/ 2) * ( log ( [ Zn++ ] / [Cu++ ] )
E = 1.1 – (0.02955) * ( log ( [ 200 ] / [1 ] )
E = 1.1 – (0.02955) * ( log ( [ 200] )
E = 1.1 – (0.02955) * ( log ( [ 2] )
E = 1.1 – (8.8 *10-3)
E = 1.091 v

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6- Calculate EMF of the following cell if E Zn++→Zn = -0.76


Zn(s) |Zn++ (aq, 0.1M) ||Zn++ (aq, 1.0M) |Zn(s)

1-Half reactions and make the Balance


A-Oxidation Zn++ + 2e- → Zn E°= -0.76 v
Zn → Zn++ + 2e- E°= 0.76 v
B-Reduction Zn++ + 2e- → Zn E°= -0.76 v

2-Net equation ..... → .....

3- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (-0.76) – (-0.76) = ZERO v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (-0.76) + (0.76) = ZERO v

Dependence of Cell Potential on Concentration


4- Nernest Equation
0.0591
E = E - log( Q)
n
E = 0 – (0.0591/ 2) * ( log ( [ Zn++ 0.1 M] / [Zn++ 1 M] )
E = 0 – (0.02955) * ( log ( [ 0.1 ] / [1 ] )
E = 0 – (0.02955) * ( log ( [ 0.1] )
E = 0 – (0.02955) * ( -1 )
E = 0.02955 v

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7- Calculate the [Cu++] / [Zn++] ratio at which the following reaction will
become spontaneous at 25°C.
Cu(s) + Zn++ (aq) → Cu++ (aq) + Zn(s)

Reaction to become spontaneous it have to be a galvanic cell, so that the E have a + ve


value
1-Half reactions and make the Balance
A-Oxidation Cu+++ 2 e- → Cu E°= 0.34 v
Cu → Cu+++ 2 e- E°= -0.34 v
B-Reduction Zn++ + 2e- → Zn E°= -0.76 v

2-Net equation Cu + Zn++ → Zn + Cu++

3- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (-0.76) – (0.34) = -1.1 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (-0.76) + (-0.34) = -1.1 v

Dependence of Cell Potential on Concentration


4- Nernest Equation
0.0591
E = E - log( Q)
n
E = -1.1 – (0.0591/ 2) * ( log ([Cu++ ] / [ Zn++ ]))
E = -1.1 – (0.02955) * ( log ([Cu++ ] / [ Zn++ ]))
E have a + ve value
-1.1 – (0.02955) * ( log ([Cu++ ] / [ Zn++ ])) > zero
-1.1 > (0.02955) * ( log ([Cu++ ] / [ Zn++ ]))
-1.1 / 0.02955 > ( log ([Cu++ ] / [ Zn++ ]))
-37.225 > ( log ([Cu++ ] / [ Zn++ ]))
10-37.225 > ([Cu++ ] / [ Zn++ ])

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8- Consider the following half reactions


MnO4-(aq) + 8 H+(aq) + 5e- → Mn++(aq) + 4 H2O (L) E°=1.51
NO3-(aq) + 4 H+(aq) + 3 e- → NO(g) + 2 H2O (L) E°=0.96
Predict whether NO3- ions will oxidize Mn2+ to MnO4- under standard
state conditions.

1-Half reactions
A-Oxidation Mn++(aq) + 4 H2O (L)→ MnO4-(aq) + 8 H+(aq) + 5e-
E°= -1.51 v
B-Reduction NO3-(aq) + 4 H+(aq) + 3 e- → NO(g) + 2 H2O (L)
E°=0.96 v
2-Balance the two equation
A-Oxidation 3Mn++(aq) + 12 H2O (L)→ 3MnO4-(aq) + 24 H+(aq) + 15e-
E°= -1.51 v
B-Reduction 5NO3-(aq) + 20 H+(aq) + 15 e- → 5NO(g) + 10H2O (L)
E°=0.96 v
3-Net equation
3Mn++(aq) + 2 H2O (L)+ 5NO3-(aq) → 3MnO4-(aq) + 4 H+(aq)+ 5NO(g)

4- Ecell = E(Cathod, Reduction) - E (Anode, Oxidation)


E° = (0.96) – (1.51) = -0.55 v
Ecell = E(Cathod, Reduction) + E (Anode, Oxidation)
E° = (0.96) + (-1.51) = -0.55 v

Since the value of E is –ve, so that this is an electrolytic cell

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9- How long will it take to plate out 1.0 kg Al from aq Al+++ with a current of
100.0 A? (M.wt. of Al=26.98).

1- Plate out 1.0 kg Al


2- Moles of Al = [Mass/M.wt.Al] = [1.0*1000 gm/ 26.98] = 37.0644 gmole
3-Moles of Electron Al from aq Al+++
1 gmole of Al 3 e-
37.0644 gmole ??? e-

??? e- = 3*37.0644 = 111.193 e-

4- Quantity of charge in coulombs


1e 96,485 coulombs
111.193 e ??? coulombs

??? coulombs = 96,485*111.193 = 10,728,502.59451 coulombs

5-Current and time


Ampere= Coulombs / sec
100.0 A= 10,728,502.59451 coulombs / ??? sec
??? sec = 10,728,502.59451 coulombs / 100 A
??? sec = 10,728,5.02 sec
Time ≈ 30 hr

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10- What mass of Co from aq Co++ can be produced in 1.0 h with a current of
15 A? (M.wt. of Co= 59).

See page 866, in CHEMISTRY ZUMDAHL|ZUMDAHL BOOK QUESTION


NO.91.a

11-An unknown metal M is electrolyzed. It took 74.1 s for a current of 2.00 A


to plate out 0.107 g of the metal from a solution containing M(NO3)3.
Identify the metal.

See page 866, in CHEMISTRY ZUMDAHL|ZUMDAHL BOOK QUESTION


NO.93

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