Example 21-1A (page 828)

E
o o
o o
H2C2O4/CO2
E
o
Write the overall equation for the redox reaction that
occurs in the voltaic cell
Sc(s)|Sc
3
(aq)|| !"

(aq)|!"(s)
reaction at anode# Sc(s) 6 Sc
3
(aq) 3 e
$
reaction at cathode# !"

(aq) e
$
6 !"(s) %3
overall reaction# Sc(s) 3 !"

(aq) 6 Sc
3
(aq) 3 !"(s)
Example 21-3A (page 833)
&n acidic solution' dichro(ate ion oxidi)es oxalic acid'
H
2
C
2
O
4
(aq)' to car*on dioxide +ith a standard cell
,otential of -./- 0. 1eter(ine the standard reduction
,otential for the CO
2
(")/H
2
C
2
O
4
(aq) electrode.
2$
$ 3
Cr
2
O
2
(aq) -4 H (aq) 3 e

6 2 Cr (aq) 2 H
2
O(l)
$
H
2
C
2
O
4
(aq) 6 2 CO
2
(") 2 H
overall reaction#
2$
(aq) 2 e %3

Cr
2
O
2
(aq) 3 H
2
C
2
O
4
(aq) / H
6 2 Cr
3
(aq) 3 CO
(aq)
2
(") 2 H
2
O(l)
cell
4 E
cathode
$ E
anode
4 E
Cr2O22$/Cr3
$ E
o
H2C2O4/CO2
-./- 0 4 -.33 0 $ E
o
H2C2O4/CO2
4 -.33 0 $ -./- 0 4 $5.4/ 0
E
o
cell
(E
6he h7dro"en$ox7"en fuel cell is a voltaic cell +ith a cell
reaction
2 H
2
(") O
2
(") 6 2 H
2
O(l)
8se ther(od7na(ic data fro( !,,endix 1 to calculate
cell
for this reaction.
9
o
4 2 9
o
:H
O(l); $ 2 9
o
:H ("); $ 9
o
:O (");
f 2 f 2 f 2
4 2($232.-) $ 2(5) $ (5) <=/(ol
4 $424.2 <=/(ol
9
o
4 $n>E
o
E
o
4 $424.2 <=/(ol
3
cell
4 ($424.2 % -5 )/:4(?34/@); 4 -.22/ 0
o
cell
in 6a*le 2-.- is -.22? 0.)
Example 21-5A (page 836)
cell
(i.e. E
!"/!"
E
o o
4 E $ E
cell
o
Aa(e one (etal ion that Cu(s) can dis,lace fro(
aqueous solution and deter(ine E
o
for the reaction.
B if Cu(s) is to dis,lace a (etal cation fro( solution' it
(ust *e oxidi)ed to Cu
2
(aq) and the (etal cation in
solution (ust *e reduced to its corres,ondin" solid
B this ,rocess (ust *e s,ontaneous so the standard
,otential for the reduction of the (etal cation (ust *e
a*ove (i.e. (ore ,ositive than) that for Cu(s)/Cu
2
(aq)
o
cu2/cu
4 5.345 0)
B onl7 ,rocess fits this condition in 6a*le 2-.- is the
reduction of !"

(aq) to !"(s) (E
o
4 5./55 0)
cell
4 E
cathode
$ E
o
anode
o
!"/!"
o
cu2/cu
4 5./55 0 $ 5.345 0 4 5.435 0
Example 21-6A (page 836)
2$
!n inex,ensive +a7 to (a<e ,eroxodisulfates (e.". S
2
O
/
)
+ould *e to ,ass ox7"en "as throu"h an acidic solution of
sulfate. &s this (ethod feasi*le under standard
conditionsC
2$ 2$ o
oxidation# 2 SO
4
(aq) 6 S
2
O
/
2e$ %2 $E 4 $(2.5- 0)
reduction# O
2
(") 4H

(aq) 4e
$
6 2 H
2
O(l) E 4 -.22? 0
2$ 2$
overall# O
2
(") 4 SO
4
E
o
(aq) 4H (aq) 6 2 H
2
O(l) 2 S
2
O
/
cell
4 -.22? 0 $2.5- 0 4 $5.2/ 0
Since E
o
is ne"ative' ,rocess is not feasi*le.
E
o
E
o
o
Should the reaction of Sn(s) and D*
2
(aq) "o to
co(,letionC
oxidation# Sn(s) 6 Sn
2
(aq) 2 e
$
$E
o
4 $($5.-32 0)
reduction# D*
2
(aq) 2 e
$
6 D*(s) E
o
4 $5.-2@ 0
overall# Sn(s) D*
2
(aq) 6 Sn
2
(aq) D*(s)
cell
4 $5.-2@ 0 5.-32 0 4 5.5-2 0
cell
4 (E6/n>) &n F
eq
or F
eq
4 ex,(n>E
cell
/E6)
F
eq
4 ex,:(2)(?34/@)(5.5-2)/(/.3-4@%2?/.-@);
4 ex,:5.?33;
4 2.@
6his F
eq
is ver7 close to -.5 so the reaction is close to
equili*riu(. &n other +ords' it does not "o to co(,letion.
Example 21- 8 B (page 840)
2
2
2
2
Calculate E
cell
for the follo+in" voltaic cell#
Dt|Cl (- at()|Cl
$
(-.5 G)||D*
2
(5.5@5 G)'H

(5.-5G)|D*O (s)
oxidation# 2 Cl
$
(aq) 6 Cl
(") 2 e
$
$E
o
4 $(-.3@/ 0)
reduction# D*O
2
(s) 4 H

(aq) 2 e
$
6 D*
2
2 H O(l) E
o
4 -.4@@ 0
2
overall# D*O (s) 2 Cl
$
(aq) 4 H

(aq)
6 D*
2
Cl
E
o
2
(") 2 H
2
O(l)
cell
4 -.4@@ 0 $ -.3@/ 0 4 5.5?2 0
E6 E6
HD*
2
I(D )
E E
o
&nJ E
o
&n
Cl 2
cell cell
n>
cell
n> HCl I
2
HH I
4
5.5?2
(/.3-4@)(2?/.-@ )
&n
H5.5@5I (- )
(2)(?34/@) H-.5I
2
H5.-5I
4
5.5?2 5.5/5 0
5.5-2 0
E
o
>or +hat ratio of HSn
2
I/HD*
2
I +ill the cell
Sn(s)|Sn
2
(aq)||D*
2
(aq)|D*(s)
not *e s,ontaneous in either directionC
&f the cell is not s,ontaneous in either direction' it (ust *e
at equili*riu( (i.e. E
cell
4 5.555 0).
oxidation# Sn(s) 6 Sn
2
(aq) 2 e
$
$E
o
4 $($5.-32 0)
reduction# D*
2
(aq) 2 e
$
6 D*(s) E
o
4 $5.-2@ 0
overall# Sn(s) D*
2
(aq) 6 Sn
2
(aq) D*(s)
cell
4 $5.-2@ 0 5.-32 0 4 5.5-2 0
2
E E
o
E6
&nJ E
o
E6
&n
HS n I
cell cell
n>
cell
n> HD*
2
I
(/.3-4@)(2?/.-@) HSn
2
I
5.555 5.5-2 &n
(2)(?34/@) HD*
2
I
5.5-2 5.5-2/43&n
HSn
2
I
HD*
2
I
5.?34- &n
HSn
2
I
HD*
2
I
HSn
2
I
HD*
2
I
ex,(5.?34-) 2.@
Example 21- 10 B (page 844)
2
2
s,
cell
E E
2
2
Calculate the solu*ilit7 ,roduct for D*&
2
"iven the follo+in"
concentration cell infor(ation#
D*(s)|D*
2
(satd. D*&
)||D*
2
(5.-5 G)|D*(s) E
cell
4 5.5@32 0
oxidation# D*(s) 6 D*
2
(satd. D*&
) 2 e
$
reduction# D*
2
(5.-5 G) 2 e
$
6 D*(s)
overall# D*
2
(5.-5 G) 6 D*
2
(satd. D*& )
6he solu*ilit7 ,roduct under consideration is
D*&
2
(s) WD*
2
(aq) 2 &
$
(aq) F 4 HD*
2
IH&
$
I
2
Since this is a concentration cell' E
o
4 5.555 0. 8se the
Aernst equation to esta*lish the HD*
2
I in saturated D*& .
o
cell cell
E6
&nJ
n>
(/.3-4@)(2?/.-@) HD*
2
I
5.5@32 5.555 &n
sat d
(2)(?34/@) H5.-5I
4.4-32 &nHD*
2
I
satd
&nH5.-5I
&nHD*
2
I
satd
4.4-33 2.353 3.2-3
HD*
2
I
satd
ex,( 3.2-3) 5.55-2-G
H&
$
I 4 2 HD*
2
I 45.55242 G
F
s,
4 HD*
2
IH&
$
I
2
4 (5.55-2-)(5.55242)
2
4 2.- % -5
$?
(+hich is consistent +ith the ta*ulated value)
&f -2.3 " of co,,er is de,osited at the cathode of an
electrol7tic cell after @.@ h' +hat +as the current usedC
(oles of co,,er 4 -2.3 "/33.@43 " (ol
$-
4 5.-?3@3 (ol
Cu(s) ,lates out at the cathode accordin" to the reduction
Cu
2
(aq) 2 e
$
6 Cu(s)
6herefore
(oles of electrons 4 2 % (oles of co,,er 4 5.3/2-2 (ol
J 4 n> 4 it
6herefore'
i 4 n>/t
4 (5.3/2-2)(?34/@)/(@.@%35%35) !
4 -./? !