Electrochemistry

Electrochemistry page 1
1970 1972
Account for the observation that silver dissolves in 1 Br2 + 2 Fe2+(aq)  2 Br-(aq) + 2 Fe3+(aq)
molar hydroiodic acid despite the fact that the standard For the reaction above, the following data are avail-
electrode potential for the change, Ag  Ag+ + e- is – able:
0.80 volt. 2 Br-(aq)  Br2(l) + 2e- E = -1.07 volts
Answer: Fe (aq)  Fe (aq) + e-
2+ 3+
E = -0.77 volts
The standard potential is based upon [Ag +] = 1.0 M. -------------------------------------------------------------------------------------
But because AgI is insoluble (very small KSP) the con- S, cal/mole.K
centration of Ag+ never reaches 1.0 M. Therefore, the Br2(l) 58.6 Fe2+(aq) -27.1
equilibrium is shifted in favor of the production of the Br-(aq) 19.6 Fe3+(aq) -70.1
-------------------------------------------------------------------------------------
ion and the potential under these conditions is > 0
volts. (a) Determine S (b) Determine G
(c) Determine H
1970 Answer:
Why are solutions of thiosulfate for analysis not S_ S _prod . S _reactants
acidic? Refer to the following standard electrode po- (a)
tentials and write the balanced equation that would ac- = [(19.6)(2)+(-70.1)(2)]-[58.6+(-27.1)(2)] cal
count for this fact.
= -105.4 cal
E _
2 S + 6 OH-  S2O32- + 3 H2O + 4e- +0.74v (b) G = -nE = -(2)(23060cal/v)(0.30v) = -13800
S2O32- + 6 OH-  2 SO32- + 3 H2O + 4e- +0.58v cal.
S2O3 + H2O  2 SO2 + 2 H + 4e
2- + -
–0.40v (c) G = H - TS ; H = G + TS
2 S + 3 H2O  S2O32- + 6 H+ + 4e- –0.50v
= -13800 + (298)(-105.4) = -45.4 kcal
Answer:
S2O32- + 6 H+ + 4e-  2 S + 3 H2O E = +0.50v
1973 B
S2O3 + H2O  2 SO2 + 2 H + 4e
2- + -
E = –0.40v
--------------------------------------------------------------- Sn + 2 Ag+  Sn2+ + 2 Ag
2 S2O32- + 4 H+  2 S + 2 H2O + 2 SO2 E = +0.10v (a) Calculate the standard voltage of a cell involving
The thiosulfate decomposes into sulfur, water, and sul- the system above.
fur dioxide. (b) What is the equilibrium constant for the system
above?
1971
Quantitative chemical data are often based on arbitrary (c) Calculate the voltage at 25C of a cell involving
standards. Discuss this statement with the following the system above when the concentration of Ag + is
data for fluorine 0.0010 molar and that of Sn2+ is 0.20 molar.
(a) The atomic weight of fluorine is 19.00 Answer:
(b) E, the standard electrode potential, is +2.65 volts (a) E = [0.80v - (-0.14v)] = 0.94v
0 . 0592
for the half reaction: F2 + 2e-  2 F- E  log K OR  nFE  RT ln K
(b) n
Answer:
0 . 94 2 31
(a) The atomic mass of fluorine is 19.00 times the log K   31 . 8 ; K  6 1 0
mass of 1/12 of the mass of a carbon-12 atom. 0 . 0592
Carbon-12 has been given the standard atomic RT [ Sn 2  ]
E  E _ ln Q ; Q 
mass of 12.000… nF [ Ag ]
 2
(c)
(b) the fluorine/fluoride potential is 2.65 v better than 0 . 0592 0 . 20
the half reaction, 2 H+ + 2 e-  H2, which has been E  0 . 94  log 2  0 . 81 v
2 ( 0 . 0010 )
given a value of 0.00 v.
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1974 B half cells are joined by a salt bridge and the two
A steady current of 1.00 ampere is passed through an metal strips are joined by a wire.
electrolytic cell containing a 1 molar solution of (c) Calculate the final concentration of copper ion,
AgNO3 and having a silver anode and a platinum cath- Cu2+, in the cell described in part (b) if the cell
ode until 1.54 grams of silver is deposited. were allowed to produce an average current of 1.0
(a) How long does the current flow to obtain this de- ampere for 3 minutes 13 seconds.
posit? Answer:
(b) What weight of chromium would be deposited in a (a) E = 0.76 + 0.34 = 1.10 volts
second cell containing 1–molar chromium(III) ni-
G = -nE = - (2)(23.06kcal/v)(1.10v) = -50.7
trate and having a chromium anode and a platinum
kcal
cathode by the same current in the same time as
0 . 0591 0 . 0591 0 . 10
was used in the silver cell? E  E _ log Q 1 . 10  log
(b) n 2 0 . 010
(c) If both electrodes were platinum in this second
cell, what volume of O2 gas measured at standard = 1.07 v
temperature and pressure would be released at the (c) (1.0 amp)(193 sec.)(1 farad./96500 coul) =
anode while the chromium is being deposited at
the cathode? The current and the time are the = 0.0020 faraday
same as in (b) 0.0020 faraday/2 = 0.0010 mol Cu2+ reduced
Answer: (0.0050 - 0.0010) mol = 0.0040 mol Cu 2+ remain-
(a) ing
1 . 54 gAg 1 mol A g 1 mol e  96500 amp sec
    0.0040 mol / 0.500 L = 0.0080 M final [Cu2+]
1 . 00 amp 107.9gAg 1 mol A g 
1 mol e
= 1380 sec. 1978 B
1 mol A g 1 mol e  1 mol Cr 3+ (a) When 300.0 milliliters of a solution of 0.200 mo-
1 . 54 gAg    
 lar AgNO3 is mixed with 100.0 milliliters of a
107.9gAg 1 mol A g 3 mol e
(b) 0.0500 molar CaCl2 solution, what is the concen-
52.0 g C r tration of silver ion after the reaction has gone to
 3   0 . 24 7 g Cr
1 mol Cr completion?
(c) 2 H2O  O2 + 4 H+ + 4e- (b) Write the net cell reaction for a cell formed by
1 mol A g 1 mol e  1 mol O 2 placing a silver electrode in the solution remaining
1 . 54 gAg    
 from the reaction above and connecting it to a
107.9gAg 1 mol A g 4 mol e
standard hydrogen electrode.
22.4 L O 2
  0 . 0779 L O 2 (c) Calculate the voltage of a cell of this type in
1 mol O 2
which the concentration of silver ion is 410-2 M.
(d) Calculate the value of the standard free energy
1976 B
change G for the following half reaction:
(a) Calculate the value of G for the standard cell re-
Ag+ (1M) + e-  Ag
action
Answer:
Zn + Cu2+(1M)  Zn2+(1M) + Cu
(a) Ag+ + Cl-  AgCl
(b) One half cell of an electrochemical cell is made by
placing a strip of pure zinc in 500 milliliters of mol Ag+ added = (0.300 L)(0.200 mol/L) =
0.10 molar ZnCl2 solution. The other half cell is = 0.0600 mol
made by placing a strip of pure copper in 500 mol CaCl2 added = (0.100 L)(0.0500 mol/L) =
milliliters of 0.010 molar Cu(NO3)2 solution. Cal-
= 0.00500 mol
culate the initial voltage of this cell when the two
mol Cl- added = 2(0.00500 mol) = 0.0100 mol
mol Ag remaining = 0.0600 - 0.0100 = 0.0500
+ 2 
0 . 0591 [M ]
mol  0 . 740  log 2 
n [ Cu ]
 0 . 0500 mol
[Ag ] remaining   0 . 125 M 0 . 0591 1 . 80
0 . 400 L  0 . 740  log  0 . 712 v
2 0 . 20
(b) H2 + 2 Ag  2 H + 2 Ag
+ +
0 . 0591
(c) At equilibrium, Ecell = 0
E  E _ log Q ; E_ 0.80 volts 0 . 0591 [ M 2  ]
(c) n
E cell  0  E _ log 2 
n [ Cu ]
[ H  ] 2 1
Q    625
[ Ag
 2
] ( PH ) ( 4 10
2 2
) 0 . 0591 [ M 2  ]
2 E _ log 2 
n [ Cu ]
E = (0.80 - 0.08) v = 0.72 volt
(d) G = -nE = -(1)(96.5kJ/mol)(0.80v) = -77 kJ [ M 2  ] E _n ( 0 . 0740 )( 2 )
or -18 kcal
log 2   0 . 0591  0 . 0591
 25 . 0
[ Cu ]
1980 B [ M 2  ] 25
2  1 10
M(s) + Cu (aq)  M (aq) + Cu(s)
2+ 2+
[ Cu ]
For the reaction above E = 0.740 volt at 25C
(a) Determine the standard electrode potential for the 1981 D
reduction half reaction: A solution of CuSO4 was electrolyzed using platinum
M2+(aq) + 2e-  M(s) electrodes by passing a current through the solution.
(b) A cell is constructed in which the reaction above As a result, there was a decrease in both [Cu 2+] and the
occurs. All substances are initially in their stan- solution pH; one electrode gained in weight a gas was
dard states, and equal volumes of the solutions are evolved at the other electrode.
used. The cell is then discharged. Calculate the (a) Write the cathode half reaction that is consistent
value of the cell potential E, when [Cu2+] has with the observations above.
dropped to 0.20 molar. (b) Write the anode half reaction that is consistent
(c) Find the ratio [M2+]aq/[Cu2+]aq when the cell reac- with the observations above.
tion above reaches equilibrium. (c) Sketch an apparatus that can be used for such an
Answer: experiment and label its necessary components.
(a) M(s)  M2+(aq) + 2e- Xv (d) List the experimental measurements that would be
Cu (aq) + 2e-  Cu(s)
2+
0.340 v needed in order to determine from such an experi-
--------------------------------------------------------- ment the value of the faraday.
Cu2+(aq) + M(s)  M2+(aq) + Cu(s) 0.740 v Answer:
X (oxid. potential) = 0.740 v - 0.340 v = 0.400 v (a) Cu2+ + 2e-  Cu
M2+(aq) + 2e-  M(s) E = -0.400 v (b) 2 H2O  O2 + 4 H+ + 4e-
(b) M + Cu2+  M2+ + Cu (c)
initial: 1.00 M 1.00 M
change: -0.80 M +0.80 M
final: 0.20 M +1.80 M
0 . 0591
E cell  E _ log Q
n
D.C. when the H2 is burned.
power
supply 1983 C
anode cathode Ti3+ + HOBr  TiO2+ + Br- (in acid solution)
(a) Write the correctly balanced half-reactions and net
deposited Cu ionic equation for the skeletal equation shown
CuSO 4 solution above.
(b) Identify the oxidizing agent and the reducing
O2 Pt agent in this reaction.
(d) current; time; mass of cathode before and its mass (c) A galvanic cell is constructed that utilizes the re-
after passage of current - or - volume of O 2 reaction above. The concentration of each species is
leased with its temperature and pressure. 0.10 molar. Compare the cell voltage that will be
observed with the standard cell potential. Explain
your reasoning.
1982 B
When a dilute solution of H2SO4 is electrolyzed, O2(g) (d) Give one example of a property of this reaction,
is produced at the anode and H2(g) is produced at the other than the cell voltage, that can be calculated
cathode. from the standard cell potential, E. State the rela-
(a) Write the balanced equations for the anode, cath- tionship between E and the property you have
ode, and overall reactions that occur in this cell. specified.
Answer:
(b) Compute the coulombs of charge passed through
the cell in 100. minutes at 10.0 amperes. (a) Ti3+ + H2O  TiO2+ + 2 H+ + e-
(c) What number of moles of O2 is produced by the H+ + HOBr + 2e-  Br- + H2O
cell when it is operated for 100. minutes at 10.0 2 Ti3+ + HOBr + H2O  2 TiO2+ + 3 H+ + Br-
amperes? (b) HOBr is the oxidizing agent and Ti3+ is the reduc-
(d) The standard enthalpy of formation of H 2O(g) is - ing agent.
242 kilojoules per mole. How much heat is liber- (c) The observed voltage will be greater than the E
ated by the complete combustion, at 298K and value since:
1.00 atmospheres, of the hydrogen produced by 0 . 059 3
the cell operated as in (c)? E  E _ log( 0 . 1 )
2
Answer:
(d) Identification of a property from the group: G, K,
(a) cathode: 2 H2O + 2e-  H2 + 2 OH- pH
or 2 H+ + 2e-  H2
(e) G = -nE or E = log K
anode: 2 H2O  O2 + 4 H+ + 4e- 1985 B
or 2 O2–  O2 + 4e-
(a) Titanium can be reduced in an acid solution from
overall: 2 H2O  2 H2 + O2 TiO2+ to Ti3+ with zinc metal. Write a balanced
sec
equation for the reaction of TiO2+ with zinc in acid
(b) (10.0amp)(10.0 min)(60 min ) = 6.00104 coul. solution.
4 1mol e - 1mol O 2
6.00 10 coul    (b) What mass of zinc metal is required for the reduc-
(c) 96489 coul. 4 mol e - tion of a 50.00 millilitre sample of a 0.115 molar
=0.155 mol O2 solution of TiO2+?
(d) from Hf for H2O: (c) Alternatively, the reduction of TiO2+ to Ti3+ can be
H2(g) + 1/2 O2(g)  H2O(g) H = -242 kJ carried out electrochemically. What is the mini-
2 mol H 2 O 242 kJ mum time, in seconds, required to reduce another
0 . 155 mol O 2    75 . 0 kJ
1 mol O 2 1 mol H 2 O
50.000 millilitre sample of the 0.115 molar TiO 2+
(a) How many faradays were passed through the solu-
solution with a direct current of 1.06 amperes? tion?
(d) The standard reduction potential, E, for TiO2+ to (b) Write a balanced half-reaction for the process that
Ti3+ is +0.060 volt. The standard reduction poten- occurred at the cathode during the electrolysis.
tial, E, for Zn2+ to Zn(s) is -0.763 volt. Calculate (c) Write a balanced net ionic equation for the reac-
the standard cell potential, E, and the standard tion that occurred during the titration with potas-
free energy change, G, for the reaction de- sium permanganate.
scribed in part (a). (d) Calculate the molarity of the KMnO4 solution.
Answer: Answer:
(a) Zn  Zn2+ + 2e- (a) (1.100 hr)(3600 sec/hr) = 3960 sec.
2 TiO2+ + 4 H+ + 2e-  2 Ti3+ + 2 H2O (3960 sec)(0.125 amp) = 495 coul
------------------------------------------------------------------------------ 1 farad
2 TIO2+ + 4 H+ + Zn  Zn2+ + 2Ti3+ + 2 H2O
495 coul  96500 coul = 5.1310-3 faraday
0.115 mol TiO 2 + 1 mol Zn
2+ (b) Fe3+ + 1e-  Fe2+
(b) 0.0500 L  1L  1 mol TiO 
(c) MnO4- + 8 H+ + 5e-  Mn2+ + 4 H2O
65.4 g Zn
1 mol Zn
5 Fe2+  5 Fe3+ + 5e-
= 0.188 g Zn ---------------------------------------------------------------------------------
0.115mol TiO 2 
1mol e  MnO4- + 8 H+ + 5 Fe2+  5 Fe3+ + Mn2+ + 4 H2O
0.500L  
1L 1mol TiO 2  1 mol Fe 2  1 mol MnO -4
(c) 5 . 13 1 0
3
farad   2 
96500coul 1 amp sec 1 1 f arad 5 mol Fe
    523 sec. (d)
1mol e  1 coul. 1.06 amp 1 
  0 . 0416 M MnO 4
0 . 02465 L
(d) Zn  Zn2+ + 2e- E = 0.763 v
2TiO2+ + 4H+ + 2e-  2Ti3+ + 2H2O E = 0.060 v
1987 D
E = 0.823 v A dilute solution of sodium sulfate, Na 2SO4, was elec-
G = -nE trolyzed using inert platinum electrodes. In a separate
96500 coul 0 . 823 v 1J experiment, a concentrated solution of sodium chlo-

 2 mo l e  
   ride, NaCl, was electrolyzed also using inert platinum
1 mo l e 1 1 v coul
electrodes. In each experiment, gas formation was ob-
= -1.59105 J served at both electrodes.
(a) Explain why metallic sodium is not formed in ei-
1986 B ther experiment.
A direct current of 0.125 ampere was passed through (b) Write balanced equations for the half–reactions
200 millilitres of a 0.25 molar solution of Fe 2(SO4)3 be- that occur at the electrodes during electrolysis of
tween platinum electrodes for a period of 1.100 hours. the dilute sodium sulfate solution. Clearly indicate
Oxygen gas was produced at the anode. The only which half–reaction occurs at each electrode.
change at the cathode was a slight change in the color
(c) Write balanced equations for the half–reactions
of the solution.
that occur at the electrodes during electrolysis of
At the end of the electrolysis, the electrolyte was acidi-
the concentrated sodium chloride solution. Clearly
fied with sulfuric acid and was titrated with an aqueous
indicate which half–reaction occurs at each elec-
solution of potassium permanganate. The volume of
trode.
the KMnO4 solution required to reach the end point
was 24.65 millilitres.
(d) Select two of the gases obtained in these experi- 0 . 0592
E  log K OR  nFE  RT ln K
ments, and for each gas, indicate one experimental (c) n
procedure that can be used to identify it. 0 . 94 2 31
log K   31 . 8 ; K  6 1 0
Answer: 0 . 0592
(a) Na+ is not reduced as easily as H 2O (or H+ or OH–). RT [ Sn 2  ]
OR E  E _ ln Q ; Q   2
nF [ Ag ]
If Na(s) were formed, it would rapidly react with (d)
water to reform Na+. 0 . 0592 1
E  0 . 94  log 2  0 . 84 v
(b) Anode: 2 H2O  O2 + 4 H+ + 4e- 2 ( 0 . 02 )
cathode: 2 H2O + 2e-  H2 + 2 OH-
1989 B
or: 2 H+ + 2e-  H2
The electrolysis of an aqueous solution of potassium
(c) anode: 2 Cl-  Cl2 + 2e- iodide, KI, results in the formation of hydrogen gas at
cathode: 2 H2O + 2e-  H2 + 2 OH- the cathode and iodine at the anode. A sample of 80.0
or: 2 H+ + 2e-  H2 millilitres of a 0.150 molar solution of KI was elec-
trolyzed for 3.00 minutes, using a constant current. At
(d) H2 - “pop” with a lit splint; O 2 - ignites a glowing the end of this time, the I2 produced was titrated
splint; Cl2 - yellowish-green color against a 0.225 molar solution of sodium thiosulfate,
(other suitable tests accepted) which reacts with iodine according to the equation be-
low. The end point of the titration was reached when
1988 B 37.3 millilitres of the Na2S2O3 solution had been added.
An electrochemical cell consists of a tin electrode in an I2 + 2 S2O32-  2 I- + S4O62-
acidic solution of 1.00 molar Sn2+ connected by a salt (a) How many moles of I2 was produced during the
bridge to a second compartment with a silver electrode electrolysis?
in an acidic solution of 1.00 molar Ag+. (b) The hydrogen gas produced at the cathode during
(a) Write the equation for the half–cell reaction oc- the electrolysis was collected over water at 25C
curring at each electrode. Indicate which half–re- at a total pressure of 752 millimetres of mercury.
action occurs at the anode. Determine the volume of hydrogen collected. (The
(b) Write the balanced chemical equation for the vapor pressure of water at 25C is 24 millimetres of mer-
overall spontaneous cell reaction that occurs when cury.)
the circuit is complete. Calculate the standard (c) Write the equation for the half–reaction that oc-
voltage, E, for this cell reaction. curs at the anode during the electrolysis.
(c) Calculate the equilibrium constant for this cell re- (d) Calculate the current used during the electrolysis.
action at 298K. Answer:
(d) A cell similar to the one described above is con- 0 . 225 molS 2 O 23  1 mol I 2
0 . 0373 L   2  
structed with solutions that have initial concentra- 1L 2 mol S 2 O 3
tions of 1.00 molar Sn2+ and 0.0200 molar Ag+. (a)
Calculate the initial voltage, E, of this cell. = 4.2010-3 mol I2
Answer: (b) PH2 = Ptotal - PH2O
(a) Sn  Sn2+ + 2e- anode reaction = (752 - 24) mm Hg = 728 mm Hg
Ag+ + e-  Ag 1 mol H2 = 1 mol I2
(b) 2 Ag+ + Sn  2 Ag + Sn2+ PV = nRT ; V = nRT/P
E = [0.80v - (-0.14v)] = 0.94v ( 4 . 20 10  3 mol )0 . 0821 Latm
mol K ( 298 K )
V  728 
( 760 ) atm
= 0.107 L An unknown metal M forms a soluble compound,
(c) At anode: 2 I–  I2 + 2e- M(NO3)2.
2 mol e  96489 amp sec (a) A solution of M(NO3)2 is electrolyzed. When a
 3
4 . 20 1 0 mo l I 2   
 constant current of 2.50 amperes is applied for
1 mol I 2 1 mol e
(d) 35.0 minutes, 3.06 grams of the metal M is de-
1 min 1 posited. Calculate the molar mass of M and iden-
   4 . 5 0 amp
60 sec. 3 min . tify the metal.
(b) The metal identified in (a) is used with zinc to
1991 D construct a galvanic cell, as shown below. Write
Explain each of the following. the net ionic equation for the cell reaction and cal-
(a) When an aqueous solution of NaCl is electrolyzed, culate the cell potential, E.
Cl2(g) is produced at the anode, but no Na (s) is pro-
duced at the cathode. + -
K Cl
(b) The mass of Fe(s) produced when 1 faraday is
used to reduce a solution of FeSO 4 is 1.5 times the M e ta l
mass of Fe(s) produced when 1 faraday is used to M Z in c
reduce a solution of FeCl3.
(c) Zn + Pb2+ (1–molar)  Zn2+ (1–molar) + Pb
The cell that utilizes the reaction above has a 1 .0 M M ( N O 3) 2 1 . 0 M Z n S O4
higher potential when [Zn2+] is decreased and
[Pb2+] is held constant, but a lower potential when (c) Calculate the value of the standard free energy
[Pb2+] is decreased and [Zn2+] is held constant. change, G, at 25C for the reaction in (b).
(d) The cell that utilizes the reaction given in (c) has (d) Calculate the potential, E, for the cell shown in (b)
the same cell potential as another cell in which if the initial concentration of ZnSO4 is 0.10-molar,
[Zn2+] and [Pb2+] are each 0.1–molar. but the concentration of the M(NO 3)2 solution re-
Answer: mains unchanged.
(a) Cl– is more easily oxidized than water Answer:
water is more easily reduced than Na+ 1 mol e  60 sec. 35 . 0 min
2 . 50 amp    
(b) Fe2+ req. 2 farad/mol Fe(s) or 1 farad  1/2 mol Fe(s) 96500 amp sec 1 min . 1
(a)
Fe3+ req. 3 farad/mol Fe(s) or 1 farad  1/3 mol Fe(s) 1 mol M  2
  2 . 72 1 0 mol
for equal numbers of farad 1/2:1/3 :: 1.5:1 2 mol e

(c) using LeChatelier’s principle

3.06 g/2.7210-2 mol = 112 g/mol;  metal is Cd
if [Zn ] , reaction shifts ,  cell potential 
2+
(b) Zn  Zn2+ + 2e- E = +0.76 v
if [Pb ] , reaction shifts ,  cell potential 
2+
Cd + 2e-  Cd
2+
E = –0.40 v
or using the Nernst Equation ------------------------------------------
Ecell = E - RT lnQ, where Q = [Zn2+]/[Pb2+], Cd2+ + Zn  Cd + Zn2+ E = +0.36 v

if [Zn2+] , Q<1, Ecell > E (c) G = -nE = -(2)(96.5 kJ/v)(0.36v) = -69 kJ
if [Pb2+] , Q>1, Ecell < E 0 . 0592 [ Zn 2  ]
E cell  E _ log 2 
(d) [Zn2+]/[Pb2+] does not change regardless of the val- n [ Cd ]
(d)
ues,  Ecell = E
0 . 0592 0 . 10
or [Zn2+]/[Pb2+] = 1; ln Q = 0; Ecell = E E cell  0 . 36 v  log  0 . 39 v
2 1
1992 B
1993 D states. The value of the equilibrium constant, Keq, for
A galvanic cell is constructed using a chromium elec- the reaction is 4.21017 at 25C.
trode in a 1.00-molar solution of Cr(NO3)3 and a cop- (a) Predict the sign of the standard cell potential, E,
per electrode in a 1.00-molar solution of Cu(NO3)2. for a cell based on the reaction. Explain your pre-
Both solutions are at 25C. diction.
(a) Write a balanced net ionic equation for the sponta-
(b) Identify the oxidizing agent for the spontaneous
neous reaction that occurs as the cell operates.
reaction.
Identify the oxidizing agent and the reducing
agent. (c) If the reaction were carried out at 60C instead of
(b) A partial diagram of the cell is shown below. 25C, how would the cell potential change? Jus-
tify your answer.
(d) How would the cell potential change if the reac-
tion were carried out at 25C with a 1.0-molar so-
lution of Mg(NO3)2 and a 0.10-molar solution of
Sr(NO3)2 ? Explain.
(e) When the cell reaction in (d) reaches equilibrium,
Cr Cu what is the cell potential?
Answer:
(a) (+); K > 1 OR reaction is spontaneous OR E for
Sr2+ is more positive OR E for Sr is more nega-
1 .0 M C r (N O 3) 3 1 .0 M C u (N O 3) 3 tive OR E = +0.52 v
(i) Which metal is the cathode? (b) Mg2+
RT
(ii) What additional component is necessary to
make the cell operate? (c) increase; E = n  ln Keq, as T increases so does
(iii) What function does the component in (ii) E .
serve? 0.0257 0.10
(c) How does the potential of this cell change if the (d) increase; Ecell = E – n ln Q, when Q = 1
concentration of Cr(NO3)3 is changed to 3.00-mo- then Ecell becomes larger.
lar at 25C? Explain.
OR an explanation using LeChâtelier’s Principle.
Answer:
(e) Ecell = 0
(a) 2 Cr + 3 Cu2+  2 Cr3+ + 3 Cu
Cr = reducing agent; Cu2+ = oxidizing agent 1997 B
(b) (i) Cu is cathode In an electrolytic cell, a current of 0.250 ampere is
(ii) salt bridge passed through a solution of a chloride of iron, produc-
(iii) transfer of ions or charge but not electronsing Fe(s) and Cl2(g).
(c) Ecell decreases. (a) Write the equation for the half-reaction that occurs
at the anode.
use the Nernst equation to explain answer
(b) When the cell operates for 2.00 hours, 0.521 gram
of iron is deposited at one electrode. Determine
1996 D
the formula of the chloride of iron in the original
Sr(s) + Mg2+  Sr2+ + Mg(s)
solution.
Consider the reaction represented above that occurs at
(c) Write the balanced equation for the overall reac-
25C. All reactants and products are in their standard
tion that occurs in the cell.
(d) How many liters of Cl2(g), measured at 25C and
750 mm Hg, are produced when the cell operates
as described in part (b) ?
(e) Calculate the current that would produce chlorine
gas from the solution at a rate of 3.00 grams per
hour.
Answer:
(a) 2 Cl– – 2 e-  Cl2
(b) 0.250 amp  7200 sec = 1800 coulomb
1 mol e -
1800 coul  96500 coul = 0.0187 mol e-

1 mol Fe
55.85 g Fe Answer the following questions regarding the electro-
0.521 g Fe  = 0.00933 mol Fe chemical cell shown.
0.0187 mol e- 2
= (a) Write the balanced net-ionic equation for the
0.00933 mol Fe 1 spontaneous reaction that occurs as the cell oper-
Fe + 2e  Fe ;  FeCl2
2+ -
ates, and determine the cell voltage.
(c) Fe2+ + 2 Cl–  Fe + Cl2 (b) In which direction do anions flow in the salt
1 mol Cl 2 bridge as the cell operates? Justify your answer.
-
(d) 0.0187 mol e-  2 mol e = 0.00933 mol Cl2 (c) If 10.0 mL of 3.0-molar AgNO3 solution is added
 L • atm  to the half-cell on the right, what will happen to
( 0 . 0093 3 mol ) 0 . 0821 ( 298 K )
 mol •K
 the cell voltage? Explain.
nRT
750 atm
760  (d) If 1.0 gram of solid NaCl is added to each half-
V= P =
cell, what will happen to the cell voltage? Explain.
= 0.231 L
3.00 g Cl 2 1 hr 1 mol Cl 2 (e) If 20.0 mL of distilled water is added to both half-
  cells, the cell voltage decreases. Explain.
1 hr 3600 sec 70.906 g Cl 2
(e) Answer
2 mol e - 96500 amp sec
 (a) 2 Ag+ + 2 e-  2 Ag E = +0.80 v
1 mol Cl 2 1 mol e -
 = 2.27 amp Cd – 2 e--  Cd2+ E = +0.40 v
OR 2 Ag+ + Cd  2 Ag + Cd2+ E = +1.20v
0.00933 mol Cl 2 0.662 g Cl 2 0.331 g Cl 2
= (b) Anions flow into the cadmium half-cell. As the
2 hrs. 2 hrs. = 1 hr.
cell operates, Cd2+ cations increase in number and
0.250 amp X need to be balanced by an equal number of anion
=
0.331 g Cl 2 3.00 g Cl 2
; X = 2.27 amp charges from the salt bridge.
(c) Cell voltage will increase. An increase in silver
1998 D ion concentration will result in faster forward re-
action and a higher cell potential.
(d) Cell voltage will decrease. As the salt dissolves,
the Cl– ion will cause the Ag+ ion to precipitate as
AgCl and decrease the [Ag+]. This will result in a
slower forward reaction and a decrease in cell po-
tential. Since cadmium chloride is a soluble salt, it
will not affect the cadmium half-cell.
2+
0.0592 [Cd ] (ii) Zn(s) + Co2+(aq)  Zn2+(aq) + Co(s)
log
2 [Ag + ] 2 (iii) oxid: Zn(s) – 2 e-  Zn2+(aq) E = +0.76V
(e) E = 1.20v –
cell ; while both con-
centrations are 1.0M, the cell potential is 1.20v. red: Co2+(aq)+ 2 e-  Co(s)
E = –0.28V
But if each solution’s concentration is cut in half, +0.48V
0.0592 [.5]
log (b) (i) G = –nE = –(2)(96500)(0.55) = –106 kJ
2 [.5 ] 2
then, E = 1.20v –
cell = 1.19v (ii) Keq = e–G/RT = e–(–106150/(8.31)(298)) =
4.131018
2000 B
2. Answer the following questions that relate to elec- (iii) 2 H2O(l) + O2(g)  2 H2O2(aq) E = –0.55 V
trochemical reactions. O2(g) + 4 H+(aq) + 4 e-  2 H2O(l) E = 1.23 V
(a) Under standard conditions at 25C, Zn(s) reacts
______________________________________________________________________________________________________________________
with Co2+(aq) to produce Co(s). 2 O2(g) + 4 H+(aq) + 4 e-  2 H2O2(aq) E = 0.68 V

(i) Write the balanced equation for the oxidation divide the equation by 2 but keep the E the same.
half reaction. (d) 1.00 hr   100. amp     = 119 g Cu
(ii) Write the balanced net-ionic equation for the
overall reaction. 2001 D
(iii) Calculate the standard potential, E, for the
overall reaction at 25C.
(b) At 25C, H2O2 decomposes according to the fol-
lowing equation.
2 H2O2(aq)  2 H2O(l) + O2(g) E = 0.55 V
(i) Determine the value of the standard free en-
ergy change, G, for the reaction at 25C.
(ii) Determine the value of the equilibrium con-
stant, Keq, for the reaction at 25C.
(iii) The standard reduction potential, E, for the
half reaction O2(g) + 4 H+(aq) + 4 e-  2 Answer the following questions that refer to the gal-
H2O(l) has a value of 1.23 V. Using this in- vanic cell shown in the diagram above. (A table of
formation in addition to the information standard reduction potentials is printed on the green in-
given above, determine the value of the stan- sert and on page 4 of the booklet with the pink cover.)
dard reduction potential, E for the half reac- (a) Identify the anode of the cell and write the half re-
tion below. action that occurs there.
O2(g) + 2 H+(aq) + 2 e-  H2O2(aq) (b) Write the net ionic equation for the overall reac-
(c) In an electrolytic cell, Cu(s) is produced by the tion that occurs as the cell operates and calculate
electrolysis of CuSO4(aq). Calculate the maximum the value of the standard cell potential, Ecell .
mass of Cu(s) that can be deposited by a direct cur- (c) Indicate how the value of Ecell would be affected if
rent of 100. amperes passed through 5.00 L of the concentration of Ni(NO3)2(aq) was changed
2.00 M CuSO4(aq) for a period of 1.00 hour. from 1.0 M to 0.10 M and the concentration of
Zn(NO3)2(aq) remained at 1.0 M. Justify your an-
Answer:
swer.
(a) (i) Zn(s) – 2 e-  Zn2+(aq)
(d) Specify whether the value of Keq for the cell reac- potential, E, for the cell.
tion is less than 1, greater than 1, or equal to 1. (e) Under the conditions specified in part (d), is the
Justify your answer. reaction in the cell spontaneous? Justify your an-
Answer: swer.
2+
(a) zinc; Zn(s) Zn (aq) + 2 e – Answer:
(b) Zn(s) + Ni2+(aq)  Zn2+(aq) + Ni(s) (a) (i) AgNO3 solution
Ecell = +0.76 + (-0.25) V = +0.51 V 1.50 g Zn   
(c) decrease Ecell ; Ecell = Ecell – log Q, Q = , when = 417 mL of silver nitrate solution required to
the value of Q becomes larger than 1 then the log completely react the zinc, therefore, AgNO3 is the
Q > 1 and is subtracted from the standard potential limiting reagent.
of the cell. (ii) 250 mL AgNO3  
(d) greater than 1. All spontaneous reactions (this re-  = 0.01375 mol Zn
action is spontaneous because the cell potential is
larger than 0) have a Keq that are larger than 1, = 0.0550 M [Zn2+]
which favors the formation of products. (b) 2 Ag+ + 2e-  2 Ag E˚ = +0.80 v
Zn – 2e-  Zn2+ E˚ = +0.76 v
2002 B
+1.56 v
Answer parts (a) through (e) below, which relate to re-
actions involving silver ion, Ag+. (c) ∆G˚ = -nFE˚ = -(2)(96500)(0.46 v) = -89000 J
The reaction between silver ion and solid zinc is repre- (d) Ecell = E˚ - log
sented by the following equation. = 0.46 - log= 0.38 v
2 Ag (aq) + Zn(s)  Zn (aq) + 2 Ag(s)
+ 2+ (e) yes; any reaction is spontaneous with a positive
(a) A 1.50 g sample of Zn is combined with 250. mL voltage
of 0.110 M AgNO3 at 25˚C.
2004 D Required
(i) Identify the limiting reactant. Show calcula-
tions to support your answer.
(ii) On the basis of the limiting reactant that you
identified in part (i), determine the value of
[Zn2+] after the reaction is complete. Assume
that volume change is negligible.
(b) Determine the value of the standard potential, E˚,
for a galvanic cell based on the reaction between
AgNO3(aq) and solid Zn at 25˚C.
Another galvanic cell is based on the reaction between
Ag+(aq) and Cu(s), represented by the equation below.
At 25˚C, the standard potential, E˚, for the cell is 0.46
V.
An electrochemical cell is constructed with an open
2 Ag+(aq) + Cu(s)  Cu2+(aq) + 2 Ag(s) switch, as shown in the diagram above. A strip of Sn
(c) Determine the value of the standard free-energy and a strip of unknown metal, X are used as electrodes.
change, ∆G˚, for the reaction between Ag+(aq) and When the switch is closed, the mass of the Sn elec-
Cu(s) at 25˚C. trode increases. The half-reactions are shown below.
(d) The cell is constructed so that [Cu 2+] is 0.045 M Sn2+ (aq) + 2 e–  Sn(s) E˚ = –0.14 V
and [Ag+] is 0.010 M. Calculate the value of the
X3+(aq) + 3 e–  X(s) E˚ = ? (d) Cr
(a) In the diagram above, label the electrode that is (e) 3 Sn2+ + 2 Cr  3 Sn + 2 Cr3+
the cathode. Justify your answer. (f) (i) E˚cell = 0.60 – log ()
(b) In the diagram above, draw an arrow indicating (ii) greater; •
the direction of electron flow in the external cir-
cuit when the switch is closed.
(c) If the standard cell potential E˚cell is +0.60 V,
what is the standard potential, in volts for the
X3+/X electrode?
(d) Identify metal X.
(e) Write balanced net-ionic equation for the overall
chemical reaction occurring in the cell.
(f) In the cell, the concentration of Sn2+ is changed
from 1.0 M to 0.50 M, and the concentration of
X3+ is changed from 1.0 M to 0.10 M.
(i) Substitute all appropriate values for determin-
ing the cell potential, Ecell, into the Nernst
equation. (Do not do any calculations.)
(ii) On the basis of your response in (f) (i), will
the cell potential be greater than, less than, or
equal to E˚cell? Justify your answer.
Answer:
(a) tin electrode is the cathode; cathode is the site of
reduction (gain in electrons) and will convert
metal ions into a metal.
electron flow
cathode
(b) (see diagram)

(c) red: Sn2+ (aq) + 2 e–  Sn(s) E˚ = –0.14 V
oxid: X(s) – 3 e–  X3+(aq) E˚ = +0.74 V
E˚cell = +0.60 V
red: X3+(aq) + 3 e–  X(s) E˚ = –0.74 V

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Electrochemistry page 1

(c) using LeChatelier’s principle

Ecell = E - RT lnQ, where Q = [Zn2+]/[Pb2+], Cd2+ + Zn  Cd + Zn2+ E = +0.36 v

1800 coul  96500 coul = 0.0187 mol e-

with Co2+(aq) to produce Co(s). 2 O2(g) + 4 H+(aq) + 4 e-  2 H2O2(aq) E = 0.68 V

(b) (see diagram)

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