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Electrochemical cell

Introduction The connection between chemistry and electricity is a very old one, going back to Alessandro Volta's discovery, in 1793, that electricity could be produced by placing two dissimilar metals on opposite sides of a moistened paper. Volta s words on his discovery! "# have the pleasure of communicating to you, $ir, and through you to the %oyal $ociety, some striking results at which # have arrived in pursuing my e&periments on the electricity e&cited by the simple mutual contact of metals of different sorts...' Electrode, galvanic cell, electrolysis cell Electrode (n electronic conductor )charge carriers are electrons*, the electrode metal and an ionic conductor, electrolyte solution form an interface at which the electrode process takes place. This two or more phase system is called electrode. (n electrohemical cell contains two electrodes anode and cathode. #n general, a liquid liquid junction separates the two electrodes. The anode is the electrode where oxidation occurs. The cathode is the electrode where reduction occurs. #n an actual cell, the identity of the electrodes depends on the direction in which the net cell reaction is occurring. Types of electrodes +lectrode +&ample type
-etal metal.ion electrode #on 5 ion )redo&* electrode -etal insoluble salt electrode ;as electrode /u)s*0/u )a3* 6t)s*07e32,7e12)a3* 9g)s* 09g1/l1)s* 0:/l)a3* 6t)s*091)g* 092 )a3*
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,escription

+lectrode reaction )in

reduction direction* -etal bathed in electrolyte /u12)a3*21e4/u)s* containing its own ions. 8oble metal in contact 7e32)a3*2e47e12)a3* with solution of a redo& couple -etal in contact with its 9g1/l1)s*21e419g21/l. insoluble salt )i.s.* and a solution containing a soluble anion of the i.s. 8oble metal in contact 92)a3*2e41=191)g* with a saturated solution for a gas and contains the reduced or o&idi<ed form of the gas 1

Liquid liquid junction! )llj* $erves as a galvanic contact between the electrodes. >l? can be a porous membrane or a salt bridge. Salt bridge is an intermediate compartment filled e.g. saturated solution of :/l and fitted with porous barrier at each end. $alt bridge minimi<es the diffusion potential )li3uid ?unction potential*, that develops when any two phases )like the two solutions* are in contact. This potential, a non.thermodynamic 3uantity adds to the cell voltage and introduces a degree of uncertainity of cell voltage measurements. @ith the salt bridge, we create two li3uid ?unction potentials , but they tend to cancel each other out. Galvanic cell ( galvanic cell contains two electrodes which are separated by a ll?., therefore the electrode reactions are also separated. #n a galvanic cell the electrochemical reaction proceeds spontaneously. )That can be used as energy sources.* The ;ibbs free energy of cell reaction is negative, r G A . @ork is done by the system. Electrolysis cell 8on.spontaneous reaction is driven by an e&ternal source of current, e.g. a battery is charged.
r G A

@ork is done on the system.

Example galvanic cell The ,aniell cell contains <inc immersed in Bn12)a3* solution and copper immersed in /u12)a3* solution. The two electrodes are in galvanic contact e.g. by a salt bridge, which prevents Bn12 and /u12 ions to penetrate to the other compartment causing chemical reaction. The spontaneous processes in ,aniell cell when the two ion concentrations are almost the same Bn)s* 4 Bn12)a3* 2 1e. /u12)a3* 2 1e 4 /u)s* Binc ions enter the a3ueous phase leaving two electrons behind, so the process is oxidation and the polarity of anode is negative. /opper ions deposit to the copper taking up two electrons from metal, so the process is reduction polarity of cathode is positive. The cell diagram, sign convention The cell diagram involves instructions for setting the cell and should be in conform with the cell reaction. The sign of cell reaction potential, Ecell should always be positive. /ell diagram is constructed to show the cell reaction running in spontaneous direction, i.e. the positive ion drifts from left to right.
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#f electrons flow from the left electrode )Bn=Bn12* to the right electrode )/u=/u12* in metal leads when the cell operates in its spontaneous direction, the potential of electrode on the right will be higher than that of the left. Bn)s* 0 Bn$CD)a3* E /u$CD)a3* 0 /u)s* #n the cell diagram components are marked with their phases, vertical bars simboli<es the phase boundaries. ,ashed vertical line E for li3uid ?unction means that diffusion potential is not eliminated. Bn)s* 0 Bn$CD)a3* F /u$CD)a3* 0 /u)s* ,ouble vertical line for li3uid ?unction! F, means that diffusion potential has been eliminated. ell reaction potential
zFEcell = r G

1.

Ecell, the cell reaction potential is the potential difference between electrodes, and zFEcell is the ma&imum work can be done by the cell. The thermodynamic sign convention for spontaneous )natural* processes! r G A thus Ecell G A. Ecell is measured, 1. /urrent appro&imates <ero 4 A in the measuring electric circuit, so system does not do any work on surroundings. 1. diffusion potential, ! has been eliminated 3. cell reaction is reversible. (t the conditions given Ecell is a measure of ma&imum work the cell could do. 7rom the measured Ecell, knowing the cell reaction itself, the reaction ;ibbs free energy can be calculated. #f diffusion current should be taken into account
E "F = Ecell + d

electromotive force E-7 is measured instead of Ecell. #n this case a non. thermodynamic 3uantity is added to Ecell. #n many case d can be minimi<ed down to several milli.volts by the application of a salt bridge, and Ecell and E-7 can be taken e3ual.

@hen the cell reaction is in chemical e3uilibrium )at d# H A, dp H A*


r G = A and Ecell = A

$ystem is incapable to do any work. ell reaction The cell reaction is the sum of half cell reactions writing in spontaneous direction. /u12)a3* 2 1e 4 /u)s* Bn)s* 4 Bn12)a3* 2 1e. (dding the two processes up the result is the cell reaction. Bn 2 /u12 4 /u 2 Bn12 Ising the sign convention the potential difference
%u $n = Ecell and Ecell A

#n general, the electrode placed on the right in the cell diagram should be the cathode, than subtraction
Ecell = ( %ight ) ( >eft )

will give positive result. The real spontaneous direction depends on the actual concentration=activity values in the cell. The cell reaction can change its direction and conse3uently Ecell its sign. The proper sign can be determined by polarity measurement, by using high input resistance voltmeter. To measure E-7 of a galvanic cell we use a high input resistance voltmeter. #t does not load the cell, and only current in nano.(mper range flows.

The !ernst equation %eaction ;ibbs free energy for cell reaction
r G = r G A + '# ln)&*

1.

standard reaction ;ibbs free energy & reaction 3uotient


J

r G A

,ividing both sides by .zF F H 9KJAA / mol.1 z reaction charge number. ) z),aniell cell* H 1**
Ecell = r G A '# ln)&* zF zF

rG A A , the standard cell reaction potential = Ecell zF


A Ecell = Ecell,1

'# ln)& * zF

3.

7or the cell reaction Bn 2 /u12 4 /u 2 Bn12 in ,aniell cell +3. 3. can be given,
&= a%u a $n , a $n a%u
1+ 1+

for pure and homogeneous phases a/u H constant and aBn H constant, thus they are involved in standard term
A A Ecell = Ecell,1 +

'# a ln) /u * zF aBn

A Ecell = Ecell

a 1+ '# ln) $n * zF a%u 1+

D.

(t conditions d# H A and dp H A the 8ernst e3uation gives the relationship between Ecell and the activity ratio of electroactive components. A @hen activity values in a galvanic cell are set as & H 1, than Ecell = Ecell . Electrode potentials Ecell can be given as the difference of electrode potentials!
Ecell = /u 1+ Bn 1+ = A + /u 1+ '# '# ln a/u 1+ ) A + ln aBn 1+ * Bn 1+ zF zF

+lectrode potential is the difference between potential in the metal and the bulk of solution. #ndividual electrode potentials can not be measured, owing to formation of double layer at the interface.

7igure 1. The electric double layer Standard cell potential (t e3uilibrium and & H (a therefore
zFEcell = A

r G = A ,
'# ln ( a zF

A A = Ecell

ln ( a =

A zFEcell '#

A The measured data for Ecell serves for the calculation of e3uilibrium constant.

ell types +lectrolyte concentration cell 5 see in details, +lectrode concentration cell )li3uid state metal containing dissolved metal component, e. g. mercury containing copper* Electrolyte concentration cells @e set a cell from two identical metal electrode )-e* and an electrolyte from a soluble salt of this metal )-e2*. The -e2 activities of compartments are different, a1 and a1. -e 0 -e2)a3*, a1 F -e2)a3*, a1 0 -e

@hen ine3uality a1 L a1 holds, -e2 in the right side electrode has a greater tendency to reduce, the spontaneous processes are! %eduction )cathodic* -e2)a1* 2 e 4 -e C&idation )anodic* /ell reaction! 8ernst e3uation!
'# a

-e 4 -e2)a1* 2 e -e2)a1* 4 -e2)a1*


Ecell = a '# ln) 1 * F a1

The standard cell reaction potential is <ero.


1 #f a1 H a1 than F ln) a * = A , there is no driving force of the process, and 1 system is in chemical e3uilibrium! Ecell H A. A =A. 7rom 8ernst e3uation Ecell

a1 <1 4 a1

ln

a1 <A a1

and Ecell L A as it should be. "etal metal#ion electrode +&ample! (g)s*=(g8C3 electrode The electrochemical process which determines the electrode potential (g2 2 e. 4 (g The activity dependence of electrode potential )8ernst e3uation*
a Ag '# '# a Ag + A A (g = (g ln = (g + ln F a Ag + F a Ag

where the activity of a single component solid (g phase is unity, thus


'# A (g = (g + ln a Ag + F

(t constant temperature electrode potential depends on the silver ion activity. "etal insoluble salt electrodes /omposition! solid or li3uid metal e.g. 9g,
M

an insoluble salt of metal e.g. 9g1/l1, a c concentration electrolyte of well soluble salt of the anion e.g. :/l. Cften, the metal is covered by its insoluble salt. The electrochemical process which determines the electrode potential of calomel electrode )9g)s*09g1/l1)s* 0c):/l*a3* 9g1/l1 2 1e H 19g 2 1 /l. The concentration dependence of electrode potential )8ernst e3uation* for calomel electrode,
1 1 '# a%l a )g A cal = cal ln 1 F a )g 1 %l 1

where the activity of solid 9g and 9g1/l1phases are unity, thus


A cal = cal

'# ln a %l F

-etal insoluble salt electrodes are used as reference electrodes because they can not be polarized easily. ( current flowing through the electrode causes no change in activity of electroactive components. The solubility e3uilibrium of insoluble salt of metal stabili<es activities. +.g. for (g=(g/l=:/l electrode the value of solubility product constant, (spHN(g2ON/l.OH1.M & 1A.1A. The chloride activity is maintained either by dissolution or deposition of (g/l when polari<ation would consume or produce e&cess amount of (g2 ions.

Ion $ ion %redox& electrode ( single li3uid phase contains both the o&idi<ed and reduced forms of electrode reaction. ( noble metal electrode, e.g. 6t senses the potential difference between the bulk of solution and the metal. The electron e&change occurs in the li3uid phase. The electrochemical process which determines the electrode potential of redo& electrode 6t)s*0c7e12)a3*, c7e32)a3* 7e32 2 e H 7e12

A 7e 1+ = 7e3+ = 7e 1+ = 7e3+

'# a7e 1+ ln F aa 3 +
7e

#f

a ) Fe 3+ * =1 a ) Fe 1+ *

'# a ) Fe 3+ * ln) * =A zF a ) Fe 1+ *

The electrode potential is identical to the standard potential.


A 7e 1 + = 7e3+ = 7e 1+ = 7e3+ A 7e = +A.771 1+ = 7e 3+

V at T H 193 :.
'# a ) Fe 3 + * ln) * <A zF a ) Fe 1 + *

#f

a ) Fe

3+

a ) Fe 1 + *

<1

The electrode potential is less than the standard potential.


A 7e 1 + = 7e3+ 7e 1+ = 7e3+

The hydrogen gas electrode $ome electrode reactions involve a gaseous species such as 91, C1, or /l1. $uch reactions must also be carried out on the surface of an electrochemically inert conductor such as platinum.

7igure D. 9ydrogen gas for saturating the acidic solution. The half cell contains a liquid phase of hydrogen gas saturated acidic solution, a solid phase of platini<ed platinum electrode having high surface area,

1A

and a gas phase of a p9 1 pressure hydrogen gas in e3uilibrium with the dissolved hydrogen. The high catalytic surface of 6t catalyses the reaction 91 4 19ads and the electrode reaction between the adsorbed hydrogen atoms and hydrogen ions in solution occurs. 9alf cell reaction or electrode reaction 92 2 1e. H 1=191 The electrode potential! The 8ernst e3uation
= " s
A ) =)

'# 1 ln 1 1F a +
9

p9 1 pA

The 8ernst e3uation represents that the electrode potential of a hydrogen gas electrode depends on the activity of 92 and the pressure of 91 gas at constant temperature. #he electrochemical potential scale The reference point of potential scale! the standard hydrogen electrode. #f the pressure of 91 over the li3uid is the standard pressure p ) 1 = p A = 1 bar , we have
9 = A 9 '# 1 ln F a9 +

Standard hydrogen electrode* the zero point of electrochemical potential scale @hen the activity of hydrogen ions is the unity,
9 = A 9
A and this standard electrode potential of hydrogen electrode ) was chosen as <ero Volt for each temperature value.

#he measurement of p) /ell setup! ( second order reference half cell )ion 0insoluble salt 0metal* is attached to a hydrogen electrode.
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7igure J. The saturated calomel electrode. @hen saturated solution of :/l is used as electrolyte its electrode potential! A.1D V at 193 : vs. $9+. The half cell reaction of 9+ 192 2 1e H 91 /ell reaction 192 2 1/l. 2 1 9g H 9g1/l1 2 91 /ell diagram! 9g 0 9g1/l1)s* 0 satd. :/l sol. F c92 0 91 gas 0 6t 8ernst e3uation!
A E "F = E "F

p ) = pA a )g a )g %l '# ln 1F a 1 ) + a 1 %l
1

( ) ( )

a9g H 1, a9g1/l1 H 1 pA H p91 H 1 bar

solid phases

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A E "F = E "F +

'# ln a ) + a %l F

( ) (

) ( )

A E "F = E "F ln 1A

'# p) + ln a %l F

A A A A = ) cal = cal The standard cell reaction potential! E"F

E "F = cal ln1A

'# p) F

7or reduction of problems with li3uid ?unction and unknown activities we use reference standard p9 electrodes. The same platini<ed platinum is immersed into both solutions, and ?oined to the same secondary reference electrode. /ell with unknown p9
Eu = cal ln1A '# p) u F

/ell with reference standard )I6(/ recommended* p9


E r = cal ln1A '# p) r F

The difference between the two measured electromotive force


Eu Er = ln1A '# '# p) u + ln1A p) r F F

The unknown p9 can be given finally


p) u = p) r Eu E r '# ln1A F

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T(P>+ for standard electrode )reduction* potentials at # H 19M :, referred to $9+ 9alf reaction standard electrode potential = V . 71 2 1e H 17 1.MKK 2 (u 2 e H (u 1.K91 . /l1 2 1e H 1/l 1.3JM 2 (g 2 e H (g A.799 1+ 9g 1 + 1e = 19g A.MJ1 12 /u 2 1e H /u A.3D1 2 19 2 1e H 91 A. A by definition 12 Bn 2 1e H Bn .A.7K1 2 >i 2 e H >i .3.ADA The standard cell reaction potential of ,aniell cell is taken from table,
A A E A = %u $n = A.3D1 ) A.7K1* = 1.1AD V

1D

7igure K. The structure of glass membrane electrode. #he electrode reaction potential @ith the $9+ is on the left and the electrode to be studied is on the right the electrode reaction for a metal=metal ion electrode can be given as 1. 1. (g2 2 e H (g 92 2 e H 1=191 (g2 2 1=191 H (g 2 92 ,
) = A

1. . 1.!
Ecell = Ag )
A Ecell = Ag

'# 1 ln F a Ag

@hen a(g H 1,

A Ecell = Ag

referred to the $9+.


1J

(pplying the activity concentration relation,


A Ecell = Ag +

'# c Ag ln A F c

A Ecell = Ag +

'# '# c Ag ln + ln A F F c
'# c Ag ln A F c

Ecell = A f +

where A f is the formal potential. #emperature dependence of Ecell* E"F


r G = r ) # r S
r G = r S # p

G rG = r ) + # r #
r G = zFE "F

E zFE "F = r ) zF# "F #

E "F =

1 E r ) # "F zF #

E r ) = zF E "F # "F #
r S = rG r ) + # #

;ibbs 9elmholt< e3uation. The reaction entropy can be calculated.

"embrane equilibrium* electrochemical potential+

1K

. 7igure M. -embrane selectively permeable to water and $C 1 D

6rocesses, cathode! anode membrane Cverall process!


. . 12 /u12 2 Bn 2 $C 1 2 $C 1 D )%* 4 /u 2 Bn D )>*

/u12 2 1e. H /u Bn12 2 1e. H Bn . 1. $C 1 D ( ' ) $C D ( , )

a( $C D , ' ) > a( $C D , , )

The reaction ;ibbs free energy for the overall reaction,


r G# , p = i i
i

r G# , p = %u + $n + $C ( , ) %u $n $C ( ' )
1+ D 1+ D

The chemical potential of components take part in the process


A A /u = /u + '# ln a( %u ) = /u

A Bn = Bn

A Bn = Bn + '# ln a $n 1+
1+ 1+

A /u = /u + '# ln a %u 1+
1+ 1+

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A . $C = $C + '# ln a $C 1 D ,,
D D

A . $C = $C + '# ln a $C 1 D ,'
D D

)
( ) ( )

The reaction ;ibbs free energy given by activities


A A A 1 A r G# , p = /u + Bn + '# ln a $n 1+ + S+ '# ln a S-D , , %u '# ln %u 1+
1+

A A 1 $n S '# ln a S-D
D

( , ')

1+

A A A A r G# , p = /u + Bn %u $n + '# ln
1+ 1+

1 a $n 1+ a S-D ,, 1+ 1 a %u a S-D , '

( (

)( )(

) )

The sum of standard chemical potentials e3uals to the standard reaction ;ibbs free energy
A r G# , p = r G# , p + '# ln 1 a $n 1+ a S-D ,, 1+ 1 a %u a S-D , '

( (

)( )(

) )

8ow, we introduce the measured potential difference!


E = %u $n = r G = 1 F
1 ,' '# a %u 1+ '# a S-D E , = E A+ ln + ln 1 F a $n 1+ 1 F a S- 1 , , D membr.n

( (

) )

( (

) )

membr.n

The first two terms are identical to the electromotive force of a ,aniell cell with a salt bridge without membrane potential.
E = = %u $n
S membr.n = ' S , 1 ,' '# a S-D = ln 1 1 F a S-D , ,

( (

) )

%earranging the last e3uation and adding standard chemical potential to both sides, we get
A 1 S A 1 S S+ '# ln a S-D , , 1 F , = S+ '# ln a S-D , ' 1 F ' D D

#ntroducing electrochemical potential! = + zF

1M

S-D ( ' ) = S-D ( , )

@hen regions of different electric potentials present, there is an additive condition of e3uilibrium! electrochemical potential of charged species i must be the same in every phase. ;enerali<ation 7or dilute solutions activities can be replaced by concentrations, c
A + '# ln c1 zF1 = A + '# ln c1 zF1

divided by 8(
/# ln
c1 c = ze(1 1 ) 1 = e c1 c1 ze /#

Polt<mann distribution. 'edo0 reaction in1ol1es the participation of )2 The fumarate )7I-1.* to succinate )$I/1.* reduction 9alf reaction! CC/ /9 = /9 /CC + 19 + + 1e CC/ /9 1 /9 1 /CC +lectrons are taken from the Q bonding /ell reaction! the redo& half cell is coupled to a $9+ $9+ F 7I-1.,$I/1.,92)a1* 0 6t 9alf reaction on the left! Cverall reaction!
A E"F = E "F

192 2 1e H 91 7I-1. 2 192)a1* H $I/1. 2 92)a1*

'# a( S3% 1 ) a11 ( ) + ) p A ln 1 F a11 ( ) + ) a( F3" 1 ) p )

#n standard hydrogen electrode! a1 H 1, p)4 5 pA H 1 bar

19

'# a( S3% 1 ) E "F = E ln 1 F a11 ( ) + ) a( F3" 1 )


A "F

The organic redo& process is p9 dependent. The p9 definition!


ln ( a ( 9 + ) ) = ln 1A lg( a ( 9 + ) ) p) ln ( a 1 ( 9 + ) ) = 1 ln1A lg( a ( 9 + ) ) 1 p)

'# 1 + '# a ( S3% 1 ) E"F = E + ln a1 ( ) ) + ln 1F 1 F a( F3" 1 )


A "F

'# 1 + '# a ( S3% 1 ) E"F = E + ln a1 ( ) ) + ln 1F 1 F a( F3" 1 )


A "F

$ubstituting p9

'# '# a( S3% 1 ) E"F = E ln1A p9 + ln F 1 F a( F3" 1 )


A "F

The value of constant

M.31D R=)mol:*, it is A.AJ911 V. Cn increasing the p9 by one the electromotive force of the cell will decrease by S J9 mV.

'# ln 1A F

is given at # H 19M :, F H 9KJAA /=mol, % H

1A