ITT CHNG CH 19 Electrochemistry

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Electrochemistry
rs o U na se l U w s is e el O y n !! ly .
# #
the energy released $y a spontaneo s reaction is con%erted to electricity or electrical energy is sed to ca se a nonspontaneo s reaction to occ r
& & 2+ 2-
2Mg O2 + 4e-
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2Mg (s) + O2 (g) 2MgO (s) 2Mg2+ + 4e2O2-
Electrochemical processes are oxidation-red ction reactions in !hich"
Oxidation half-reaction (lose e-)
Reduction half-reaction (gain e-)

19.1
'he charge the atom !o ld ha%e in a molec le (or an ionic compo nd) if electrons !ere completely transferred. 1. (ree elements ( ncom$ined state) ha%e an oxidation n m$er of )ero.
2. 1n monatomic ions+ the oxidation n m$er is e2 al to the charge on the ion.
5. 'he oxidation n m$er of oxygen is usually 62. 1n /2O2 and O22- it is 61.
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*a+ ,e+ -+ .$+ /2+ O2+ .4 0 &
Oxidation n m$er
3i++ 3i 0 +14 (e5++ (e 0 +54 O2-+ O 0 -2
4.4
8. 9ro p 1: metals are +1+ 11: metals are +2 and fl orine is al!ays 61. 7. 'he s m of the oxidation n m$ers of all the atoms in a molec le or ion is e2 al to the charge on the molec le or ion.
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Oxidation n m$ers of all the atoms in /;O5- <
/;O5O 0 -2 ; 0 +4
4. 'he oxidation n m$er of hydrogen is +1 except !hen it is $onded to metals in $inary compo nds. 1n these cases+ its oxidation n m$er is 61.
/ 0 +1
5x(-2) + 1 + < 0 -1
4.4
'he oxidation of (e2+ to (e5+ $y ;r2O?2- in acid sol tion< 1. >rite the n$alanced e2 ation for the reaction ion ionic form. (e2+ + ;r2O?2(e5+ + ;r5+
2. @eparate the e2 ation into t!o half-reactions. Oxidation" (e2+

+2
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5. ,alance the atoms other than O and / in each half-reaction. ;r2O?22;r5+

19.1
(e5+ ;r5+
+5 +5
,alancing =edox E2 ations
=ed ction"
+7
;r2O?2-
4. (or reactions in acid+ add /2O to $alance O atoms and /+ to $alance / atoms. ;r2O?22;r5+ + ?/2O 14/+ + ;r2O?22;r5+ + ?/2O 8. :dd electrons to one side of each half-reaction to $alance the charges on the half-reaction. (e2+ 7e- + 14/+ + ;r2O?2(e5+ + 1e2;r5+ + ?/2O
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7. 1f necessary+ e2 ali)e the n m$er of electrons in the t!o halfreactions $y m ltiplying the half-reactions $y appropriate coefficients. 7(e2+ 7(e5+ + 7e7e- + 14/+ + ;r2O?22;r5+ + ?/2O
19.1
?. :dd the t!o half-reactions together and $alance the final e2 ation $y inspection. The number of electrons on both sides must cancel. Oxidation" 7(e2+ 7(e5+ + 7e2;r5+ + ?/2O
=ed ction" 7e- + 14/+ + ;r2O?214/+ + ;r2O?2- + 7(e2+
A. Berify that the n m$er of atoms and the charges are $alanced . 14x1 6 2 + 7x2 0 24 0 7x5 + 2x5
9. (or reactions in $asic sol tions+ add O/- to both sides of the e2 ation for e%ery /+ that appears in the final e2 ation.
19.1
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7(e5+ + 2;r5+ + ?/2O
anode oxidation
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spontaneo s redox reaction
9al%anic ;ells
cathode red ction
19.2
'he difference in electrical potential $et!een the anode and cathode is called" # cell voltage
# electromotive force (emf) # cell potential
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;ell Ciagram Dn (s) + ; E;
2+
9al%anic ;ells
(aq)
; (s) + Dn2+ (aq)
2+
F 0 1 M G EDn2+F 0 1 M
2+
Dn (s) H Dn2+ (1 M) HH ; anode
(1 M) H ; (s) cathode
19.2
Dn (s) H Dn2+ (1 M) HH /+ (1 M) H /2 (1 atm) H .t (s) ;athode (red ction)" 2e- + 2/+ (1 M) Dn (s) + 2/+ (1 M)
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:node (oxidation)"
Dn (s)
@tandard =ed ction .otentials
Dn2+ (1 M) + 2e/2 (1 atm)

19.5
Dn2+ + /2 (1 atm)
Standard reduction potential (E0) is the %oltage associated !ith a reduction reaction at an electrode !hen all sol tes are 1 M and all gases are at 1 atm.
@tandard hydrogen electrode (@/E)
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2e- + 2/+ (1 M) E0 0 & B
=ed ction =eaction /2 (1 atm)
19.5
0 Ecell 0 &.?7 B
Dn (s) H Dn2+ (1 M) HH /+ (1 M) H /2 (1 atm) H .t (s) 0+ 0 2+ 0 E 0 E E cell H /H2 Zn /Zn
Dn2+ (1 M) + 2e-
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2+ &.?7 B 0 & - E0 Zn /Zn 2+ E0 Zn /Zn 0 -&.?7 B
Dn E0 0 -&.?7 B
0 Standard emf (Ecell )
0 0 0 E cell 0 Ecathode - Eanode
19.5
0 Ecell 0 &.54 B
2+

2
0 0 2+ 0+ E cell 0 ECu /Cu 6 EH /H
&.54 0 E0 Cu2+ /Cu - &

2+ E0 Cu /Cu 0 &.54 B
.t (s) H /2 (1 atm) H /+ (1 M) HH ; ;athode (red ction)" 2e- + ; /2 (1 atm) + ;

2+
(1 M) H ; (s)
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:node (oxidation)"
/2 (1 atm)
2+
2/+ (1 M) + 2e-
(1 M)
; (s)
(1 M)
; (s) + 2/+ (1 M)
19.5
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# # # # #
E0 is for the reaction as !ritten 'he more positi%e E0 the greater the tendency for the s $stance to $e red ced 'he half-cell reactions are re%ersi$le 'he sign of E0 changes !hen the reaction is re%ersed ;hanging the stoichiometric coefficients of a half-cell reaction does not change the %al e of E0
19.5
;d2+ (aq) + 2e;r5+ (aq) + 5e-
:node (oxidation)"
;athode (red ction)" 2e- + ;d2+ (1 M) 2;r (s) + 5;d2+ (1 M)
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;r (s) E0 0 -&.?4 B ;r (s) ;d (s)
0 Ecell 0 -&.4& 6 (-&.?4) 0 Ecell 0 &.54 B
>hat is the standard emf of an electrochemical cell made of a ;d electrode in a 1.& M ;d(*O5)2 sol tion and a ;r electrode in a 1.& M ;r(*O5)5 sol tion< ;d (s) E0 0 -&.4& B ;d is the stronger oxidi)er
;d !ill oxidi)e ;r
;r5+ (1 M) + 5e- x 2 x5
5;d (s) + 2;r5+ (1 M)
19.5
9 0 -nFEcell 9 0
&
-nFE &
& 9& 0 -RT ln K 0 -nFEcell & Ecell
(A.514 IJ-#mol)(29A -) RT ln K 0 ln K 0 nF n (97+8&& IJB#mol) &.&28? B ln K n
& Ecell 0
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Ecell
&
&.&892 B log K 0 n
cell
@pontaneity of =edox =eactions
n 0 n m$er of moles of electrons in reaction
I F 0 97+8&& 0 97+8&& ;Jmol B # mol
19.4
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& 9& 0 -RT ln K 0 -nFEcell
@pontaneity of =edox =eactions
19.4
Ecell
&
Oxidation"
=ed ction" 2e- + (e2+

0 E0 0 E0 !" E Fe /Fe g" /
g
E0 0 -&.44 6 (&.A&) E0 0 -1.24 B
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&.&28? B ln K 0 n 2:g 2:g+ + 2e(e n02 K 0 1.25 x 1&-42
>hat is the e2 ili$ri m constant for the follo!ing reaction at 28&;< (e2+ (aq) + 2:g (s) (e (s) + 2:g+ (aq)
0 Ecell xn -1.24 B x 2 0 exp K 0 exp &.&28? B &.&28? B
19.4
9 0 9& + RT ln #
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E 0 E& -
9 0 -nFE 9& 0 -nFE & -nFE 0 -nFE0 + RT ln # Nernst equation RT ln # nF E 0 E0 :t 29A &.&28? B ln # n E 0 E& -
'he Effect of ;oncentration on ;ell Emf
&.&892 B log # n
19.8
Oxidation"
=ed ction" 2e- + (e2+

0 E0 0 E0 !" /Fe ECd !" Fe /Cd
E0 0 -&.44 6 (-&.4&) E0 0 -&.&4 B
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;d ;d2+ + 2e2(e n02 E 0 E& E 0 &.&15 EK& @pontaneo s
>ill the follo!ing reaction occ r spontaneo sly at 28&; if E(e2+F 0 &.7& M and E;d2+F 0 &.&1& M< (e2+ (aq) + ;d (s) (e (s) + ;d2+ (aq)
&.&28? B ln # n &.&1& &.&28? B ln E 0 -&.&4 B 2 &.7&
19.8
Leclanch cell
:node" ;athode"
Dn (s) + 2*/4 (aq) + 2MnO2 (s)
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Cry cell
Dn (s) Dn2+ (aq) + 2e2*/+ 4 (aq) + 2MnO2 (s) + 2e
,atteries
Mn2O5 (s) + 2*/5 (aq) + /2O (l)
Dn2+ (aq) + 2*/5 (aq) + /2O (l) + Mn2O5 (s) 19.7
:node" ;athode"
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Merc ry ,attery
Dn(/g) + 2O/- (aq) /gO (s) + /2O (l) + 2eDn(/g) + /gO (s) DnO (s) + /g (l)
,atteries
DnO (s) + /2O (l) + 2e-
/g (l) + 2O/- (aq)
19.7
3ead storage $attery
:node" ;athode"
2.$ (s) + .$O2 (s) + 4/+ (aq) + 2@O4 (aq)
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.$ (s) + @O24 (aq) .$@O4 (s) + 2e2.$O2 (s) + 4/+ (aq) + @O4 $aq) " 2e-
,atteries
.$@O4 (s) + 2/2O (l)
2.$@O4 (s) + 2/2O (l) 19.7
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@olid @tate 3ithi m ,attery
19.7
,atteries
:node" ;athode"
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2/2 (g) + 4O/- (aq) 4/2O (l) + 4eO2 (g) + 2/2O (l) + 4e2/2 (g) + O2 (g) 4O/- (aq) 2/2O (l)
,atteries
: fuel cell is an electrochemical cell that re2 ires a contin o s s pply of reactants to Leep f nctioning
19.7
Chemistry In Action: ,acteria .o!er
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;/5;OO- + 2O2 + /+ 2;O2 + 2/2O
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19.?
;orrosion
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;athodic .rotection of an 1ron @torage 'anL
19.?
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Electrol sis is the process in !hich electrical energy is sed to ca se a nonspontaneous chemical reaction to occ r.
19.A
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19.A
Electrolysis of >ater
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Electrolysis and Mass ;hanges
charge (;) 0 c rrent (:) x time (s) 1 mole e- 0 97+8&& ;
19.A
:node" ;athode"
2 mole e- 0 1 mole ;a
s 1 mol e- 1 mol ;a ; mol ;a 0 &.482 x 1.8 hr x 57&& x x s hr 97+8&& ; 2 mol e-
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0 &.&127 mol ;a 0 &.8& g ;a
2;l- (l) ;l2 (g) + 2e;a2+ (l) + 2e;a (s) ;a2+ (l) + 2;l- (l) ;a (s) + ;l2 (g)
/o! m ch ;a !ill $e prod ced in an electrolytic cell of molten ;a;l2 if a c rrent of &.482 : is passed thro gh the cell for 1.8 ho rs<
19.A
Chemistry In Action: Cental (illing Ciscomfort
/g2 J:g2/g5 &.A8 B @n J:g5@n -&.&8 B @n J:g5@n -&.&8 B

2+ 2+
2+
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ITT CHNG CH 19 Electrochemistry

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ITT CHNG CH 19 Electrochemistry

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Electrochemical processes are oxidation-red ction reactions in !hich"

Oxidation half-reaction (lose e-)

Reduction half-reaction (gain e-)

2. 1n monatomic ions+ the oxidation n m$er is e2 al to the charge on the ion.

3i++ 3i 0 +14 (e5++ (e 0 +54 O2-+ O 0 -2

Oxidation n m$ers of all the atoms in /;O5- <

2. @eparate the e2 ation into t!o half-reactions. Oxidation" (e2+

5. ,alance the atoms other than O and / in each half-reaction. ;r2O?22;r5+

,alancing =edox E2 ations

,alancing =edox E2 ations

=ed ction" 7e- + 14/+ + ;r2O?214/+ + ;r2O?2- + 7(e2+

,alancing =edox E2 ations

7(e5+ + 2;r5+ + ?/2O

cathode red ction

# electromotive force (emf) # cell potential

; (s) + Dn2+ (aq)

Dn (s) H Dn2+ (1 M) HH ; anode

@tandard =ed ction .otentials

Dn2+ (1 M) + 2e/2 (1 atm)

@tandard hydrogen electrode (@/E)

@tandard =ed ction .otentials

=ed ction =eaction /2 (1 atm)

Dn (s) H Dn2+ (1 M) HH /+ (1 M) H /2 (1 atm) H .t (s) 0+ 0 2+ 0 E 0 E E cell H /H2 Zn /Zn

2+ &.?7 B 0 & - E0 Zn /Zn 2+ E0 Zn /Zn 0 -&.?7 B

@tandard =ed ction .otentials

0 Standard emf (Ecell )

0 0 0 E cell 0 Ecathode - Eanode

@tandard =ed ction .otentials

0 0 0 E cell 0 Ecathode - Eanode

0 0 2+ 0+ E cell 0 ECu /Cu 6 EH /H

&.54 0 E0 Cu2+ /Cu - &

.t (s) H /2 (1 atm) H /+ (1 M) HH ; ;athode (red ction)" 2e- + ; /2 (1 atm) + ;

;d2+ (aq) + 2e;r5+ (aq) + 5e-

;athode (red ction)" 2e- + ;d2+ (1 M) 2;r (s) + 5;d2+ (1 M)

5;d (s) + 2;r5+ (1 M)

& 9& 0 -RT ln K 0 -nFEcell & Ecell

(A.514 IJ-#mol)(29A -) RT ln K 0 ln K 0 nF n (97+8&& IJB#mol) &.&28? B ln K n

@pontaneity of =edox =eactions

n 0 n m$er of moles of electrons in reaction

I F 0 97+8&& 0 97+8&& ;Jmol B # mol

@pontaneity of =edox =eactions

=ed ction" 2e- + (e2+

E0 0 -&.44 6 (&.A&) E0 0 -1.24 B

0 Ecell xn -1.24 B x 2 0 exp K 0 exp &.&28? B &.&28? B

'he Effect of ;oncentration on ;ell Emf

=ed ction" 2e- + (e2+

E0 0 -&.44 6 (-&.4&) E0 0 -&.&4 B

&.&28? B ln # n &.&1& &.&28? B ln E 0 -&.&4 B 2 &.7&

Dn (s) + 2*/4 (aq) + 2MnO2 (s)

Mn2O5 (s) + 2*/5 (aq) + /2O (l)

Dn2+ (aq) + 2*/5 (aq) + /2O (l) + Mn2O5 (s) 19.7

DnO (s) + /2O (l) + 2e-

/g (l) + 2O/- (aq)

3ead storage $attery

2.$ (s) + .$O2 (s) + 4/+ (aq) + 2@O4 (aq)

.$@O4 (s) + 2/2O (l)

2.$@O4 (s) + 2/2O (l) 19.7

Chemistry In Action: ,acteria .o!er

;athodic .rotection of an 1ron @torage 'anL

Electrolysis and Mass ;hanges

charge (;) 0 c rrent (:) x time (s) 1 mole e- 0 97+8&& ;

s 1 mol e- 1 mol ;a ; mol ;a 0 &.482 x 1.8 hr x 57&& x x s hr 97+8&& ; 2 mol e-