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Chapter 18: Electrochemistry

Basic Question 1
A galvanic cell is constructed under standard conditions using a zinc rod, dipped in a Zn+2 solution, a
copper rod dipped in a Cu+2 solution, and other necessary accessories. Answer the following
questions:
a.

What are standard conditions?


1M , 1 atm, 25C

b.

Which halfcell is assigned a potential of 0.000V?


SHE Standard Hydrogen Electrode

c.

In the above galvanic cell, which electrode is acting as the anode and which is acting as the
cathode?
Zn: Anode
Cu: Cathode

d.

Write the two halfreactions taking place.


Zn (S) Zn 2+ (aq) + 2e
Cu 2+ (aq) + 2 e - Cu (S)

d.

Which chemical is the oxidizing agent, and which is the reducing agent?
Cu2+
O.A.
Zn

R.A.

Basic Question 2
A galvanic cell that uses the following reaction:
5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
was constructed under standard conditions.
a.

Calculate E for the above cell, given the following:


Given:
= - 0.77V,
= +1.33V
RTF: E
E =

= - 0.77 + 1.33 = 0.56V

b.

Represent the above cell by a line notation.


Pt(s) Fe2+(aq), Fe3+ (aq) MnO4-(aq) , Mn2+(aq) Pt (s)

Basic Question 3
A galvanic cell that uses the following reaction:
Mg(s) + Fe2+(aq) Mg2+(aq) + Fe(s)
was constructed under standard conditions.
a.

Calculate the maximum amount of work that can be obtained from the above cell at standard
conditions, given the following:
Mg2+ + 2e- Mg
Fe2+ + 2e- Fe
E =

E = 2.37 V
E = 0.44 V
+

E0 = 2.37 0.44 = + 1.93 V


b.

Calculate G at 25C for the above reaction.


Given E0 = + 1.93 V
RTF: G0
G0 = - nFE0 = - (2)(96500)(1.93) = - 372 x 10 3 J = - 372 kJ

c.

Use your answer in (b) to indicate whether the reaction is spontaneous or not.
Since G < 0 and E > 0, the reaction is spontaneous

Basic Question 4
E for the following galvanic cell: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) is 1.1V.
Use the Nernst equation to calculate Ecell in the following case:
[Cu2+] = 0.20M, [Zn2+] = 0.30M
Given: [Cu2+] = 0.20M, [Zn2+] = 0.30M, E = 1.1V
RTF: Ecell
Ecell = Ecell
Ecell = 1.1 -

logQ = Ecell
log

= 1.09V

log

Basic Question 5
E for the following galvanic cell: Mg(s) + Cu2+(aq) Mg2+(aq) + Cu(s) is 1.1V.
Predict whether Ecell will be larger or smaller than E in the following cases:
a.
[Cu2+] = 0.20M,
[Mg2+] = 1.0M
[Cu2+] < 1.00M, by LCP the system will shift to the left, Ecell will be < E
b.

[Cu2+] = 1.0M,
[Mg2+] = 2.0M
[Mg2+] > 1.00M, by LCP the system will shift to the left, Ecell will be < E

OR
Show mathematically, using the Nernst equation if E will increase and decrease.
a) Ecell = Ecell
Q < 1,

logQ
Log Q < 0,

logQ > 0

logQ < 0

E will increase.
E > E

logQ

b) E = E
E = E
Q > 1,

logQ
Log Q > 0,

E will decrease as we are adding a negative quantity to it.


E < E

Basic Question 6
A galvanic cell is constructed using a zinc rod dipped in a 0.20M Zn+2 and another zinc rod dipped in
a 0.02M Zn+2. Answer the following questions:
a.

Which compartment will act as the anode and which will act as the cathode?
Reduction occurs in the compartment where [Zn2+] is higher (Cathode):
Zn2+(0.20M) + 2e- Zn(s)
Oxidation occurs in the compartment where [Zn2+] is lower (Anode):
Zn(s) Zn2+(0.02M) + 2e-

b.

Determine the direction of the flow of electrons for the above cell.
Electrons flow from the anode (0.02 M) compartment, to cathode (0.20 M) compartment

Basic Question 7
Calculate K for the following reaction: Zn(s) + Cu+2 (aq) Zn+2 (aq) + Cu(s) E = 1.1V.
Given: E = 1.1V
RTF:K
E =

log K

logK =

E =

(1.1) = 37.23

37

K = 1.7 10

Basic Question 8
If a steady current of 15.0 A is passed through an aqueous solution of CuSO4, how many minutes will
it take to deposit 0.250 mol of Cu at the cathode, assuming 100% efficiency?
1F = 96,485 C
Given: nCu = 0.250 moles,
RTF: time=?

I= 15.0 A,

15.0 t 1

96500 2
0.500 x 96500 = 15.0 t
0.500 96500 9650
t=
=
= 3216s
15.0
3
0.250 =

n = 2 moles

Basic Question 9
Answer the following questions about electrochemical cells.

It is observed that when silver metal is placed in aqueous nickel (II) chloride, NiCl 2, no reaction
occurs. When the switch is closed in the cell represented above, the voltage reading is +1.03 V.
(a)

Write the reduction half-reaction that occurs in the cell.


Ag+ + e Ag

(b)

Write the equation for the overall reaction that occurs in the cell.
Ni + 2Ag+ Ni2+ + 2Ag

( c)

Identify the anode in the cell. Justify your answer.


The anode is where oxidation occurs. In the overall reaction Ni is oxidized to Ni 2+, so the
anode is the Ni electrode in the left cell.

(d)

On the diagram above, use an arrow to clearly indicate the direction of current flow as the cell
operates.
The arrow should show current flow in the direction from the Ag electrode through the
wire to the Ni electrode.

(e)

Calculate the value of the standard reduction potential for the Ni+2/Ni half-reaction.
Given: E = +1.03V, E,
= +0.80V
RTF:
Ecell =

+1.03 V = +0.80V +
= + 0.23V
= - 0.23V
(f)

Assume that electrodes of pure Pt, Ag, and Tl are available as well as 1.00 M solutions of their
salts. Three different electrochemical cells can be constructed using these materials. Identify
the two metals that when used to make an electrochemical cell would produce the cell with the
largest voltage. Explain how you arrived at your answer.
E(V)
+
Tl + e Tl
0.34
+
Ag + e Ag
0.80
2+
Pt + 2 e Pt
1.20
The two metals that yield the largest Ecell are those with the biggest difference in E,
namely, Pt and Tl (see Ecell calculation below).
Ecell = +1.20 (0.34) = +1.54 V

(g)

Predict whether Pt metal will react when it is placed in 1.00 M AgNO3(aq). Justify your
answer.
When Pt metal is added to 1.00 M AgNO3, the only possible redox reaction is:
Pt(s) + 2Ag+(aq) Pt2+(aq) + 2Ag(s)
Ecell =
+
= - 1.20 + 0.80 V = 0.40 V
Because Ecell for that reaction is negative, no reaction will occur.

Basic Question 10

6Fe2+(aq) + Cr2O72(aq) + 14H+(aq) 6Fe3+(aq) + 2Cr3+(aq) + 7H2O(l)


A galvanic cell and the balanced equation for the spontaneous cell reaction are shown above. The two
reduction half-reactions for the overall reaction that occurs in the cell are shown in the table below.
Half-Reaction
E (V) at 298 K
3+

2+
Fe (aq) + e Fe (aq)
+ 0.77
2
+

3+
+1.33
Cr2O7 (aq) + 14H (aq) + 6e 2Cr (aq) + 7H2O(l)
(a)

(b)

On the diagram, clearly label the cathode.


The electrode in the beaker on the right should be labeled.
Calculate the value of the standard potential, E, for the spontaneous cell reaction.
Given:
Fe3+(aq) + e Fe2+(aq)
+ 0.77
2
+

3+
+1.33
Cr2O7 (aq) + 14H (aq) + 6e 2Cr (aq) + 7H2O(l)
RTF: Ecell
Ecell = 1.33 0.77 = 0.56 V

(c)

How many moles of electrons are transferred when 1.0 mol of Cr2O72(aq) is consumed
in the overall cell reaction?
6.0 moles of electrons are transferred.

(d)

Calculate the value of the equilibrium constant, Keq , for the cell reaction at 25C.
Given: Ecell = +0.56V

RTF: Keq
E =

log K

logK =

E =

(0.56) = 57

56

K = 7.1 10
(e)

Explain what the magnitude of Keq tells you about the extent of the reaction.
Because the magnitude of Keq is very large, the extent of the cell reaction is also very
large and the reaction goes essentially to completion.

Three solutions, one containing Fe2+ (aq), one containing Cr2O72(aq), and one containing H+(aq), are
mixed in a beaker and allowed to react. The initial concentrations of the species in the mixture are
0.70 M Fe2+(aq), 0.10 M Cr2O72(aq), and 2.0 M H+(aq).
(f)

When the reaction mixture has come to equilibrium, which species has the higher
concentration,Cr3+ (aq) or Cr2O72(aq)? Explain.
[Cr3+ (aq)] will be greater than [Cr2O72(aq)] because:
1*
as indicated in part (d), the reaction essentially goes to completion, and
2*
there is more than sufficient Fe2+ and H+ to react completely with the Cr2O72(aq).
Therefore at equilibrium, [Cr2O72(aq)] is essentially zero.

(g)

When the reaction mixture has come to equilibrium, what are the molar concentrations of
Fe2+(aq) and Fe3+ (aq)?

[initial]
[change]
[Final]

Cr2O72
0.10M
-0.10M
0

+ 14H+
2.0M
-1.4M
0.60M

+ 6Fe2+
0.70M
-0.60
0.10M

2Cr3+

+ 7H2O

+ 6Fe3+
+0.60M
0.60M

Basic Question 11
Answer the following questions related to chemical reactions involving nitrogen monoxide, NO(g).
The reaction between solid copper and nitric acid to form copper(II) ion, nitrogen monoxide gas, and
water is represented by the following equation.
3Cu(s) + 2NO3- (aq) + 8H+(aq)
(a)

3Cu2+(aq) + 2NO(g) + 4H2O(l) Ecell = +0.60 V

Using the information above and in the table below, calculate the standard reduction potential,
E, for the reduction of NO in acidic solution.

Half-Reaction
Cu2+(aq) + 2e- Cu(s)
NO3-(aq) + 4H+(aq) + 3eErxn =

NO(g) + 2H2O(l)

Standard Reduction Potential, E


+0.36V
?

+
= Erxn -

= 0.60 V (- 0.36 V) = 0.96 V

(b)

Calculate the value of the standard free energy change, G, for the overall reaction between
solid copper and nitric acid.
Given: Ecell = +0.60 V
RTF: G
G = - nFEcell = - (6)(96,500)(0.60V) = -347400J mol- = -347 kJ mol-

(c)

Predict whether the value of the standard entropy change, S, for the overall reaction is
greater than 0, less than 0, or equal to 0. Justify your prediction.
S > 0. The reaction involves the production of 2 moles of gases and 7 moles of liquid
from 3 moles of a solid and 10 moles of a liquid. Gases have very large entropies, so the
entropy will increase.

Basic Question 12
Power
supply

Ag+(aq) + le- Ag(s)

An external direct-current power supply is connected to two platinum electrodes immersed in a


beaker containing 1.0M AgNO3(aq) at 25C, as shown in the diagram above the two reduction halfreactions for the overall reaction that occurs in the cell are shown in the table below
Half-Reaction
O2(g) + 4H (aq) + 4e 2H2O(l)
Ag+(aq) + le- Ag(s)
+

E (V)
+1.23
+0.80V

a)

On the diagram indicate the direction of electron flow in the wire.


From right towards the left.

b)

Write a balanced net ionic equation for the electrolysis reaction that occurs in the cell

2H2O(l) + 4Ag + (aq) 4H+ (aq) + 4Ag(s) +O2 (g)


c)

Predict the algebraic sign of G for the reaction. Justify your answer.
G > 0, the reaction is not spontaneous

d)

Calculate the value of G for the reaction.


Given:
= +1.23V,
= +0.80V
RTF: G
E = 0.80 1.23 = -0.43V
G = - nFEcell = - (4)(96,500)(-0.43) = 165980J mol- = +166 kJ mol-

e)

An electric current of 1.50 amperes passes through the cell for 40.0 minutes
Calculate the mass of Ag(s) deposited at the electrode at 27C 1.00 atm
Given: I = 1.50A, t = 40.0min, n = 1
RTF: m of Ag
It A 1.50 x 40 x 60 108
m Ag (s) = x =
x
= 4.03g
F n
96500
1

f)

An electric current of 1.50 amperes passes through the cell for 40.0 minutes
Calculate the volume of O2(g) produced out 27C 1.00 atm
Given: I = 1.50A, t = 40.0min, n = 4, T = 27+273 = 300K, P = 1.00atm
RTF: V of O2
It A 1.50 x 40 x 60 32
mO2 = x =
x
= 0.30g
F n
96500
4

)(

)(

= 0.229 dm3