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. Voltas words on his discovery: I have the pleasure of communicating to you, Sir, and through you to the Royal Society, some striking results at which I have arrived in pursuing my experiments on the electricity excited by the simple mutual contact of metals of different sorts... Electrode, galvanic cell, electrolysis cell Electrode An 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. An electrohemical cell contains two electrodes anode and cathode. In 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. In an actual cell, the identity of the electrodes depends on the direction in which the net cell reaction is occurring. Types of electrodes Electrode Example type
Metal metal-ion electrode Ion ion (redox) electrode Metal insoluble salt electrode Gas electrode Cu(s)Cu (aq) Pt(s)Fe3+,Fe2+(aq) Hg(s) Hg2Cl2(s) KCl(aq) Pt(s)H2(g) H+ (aq)
2+

Description

Electrode reaction (in

reduction direction) Metal bathed in electrolyte Cu2+(aq)+2eCu(s) containing its own ions. Noble metal in contact Fe3+(aq)+eFe2+(aq) with solution of a redox couple Metal in contact with its Hg2Cl2(s)+2e2Hg+2Clinsoluble salt (i.s.) and a solution containing a soluble anion of the i.s. Noble metal in contact H+(aq)+e1/2H2(g) with a saturated solution for a gas and contains the reduced or oxidized form of the gas 1

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Liquid liquid junction: (llj) Serves as a galvanic contact between the electrodes. Llj can be a porous membrane or a salt bridge. Salt bridge is an intermediate compartment filled e.g. saturated solution of KCl and fitted with porous barrier at each end. Salt bridge minimizes the diffusion potential (liquid junction potential), that develops when any two phases (like the two solutions) are in contact. This potential, a non-thermodynamic quantity adds to the cell voltage and introduces a degree of uncertainity of cell voltage measurements. With the salt bridge, we create two liquid junction potentials , but they tend to cancel each other out. Galvanic cell A galvanic cell contains two electrodes which are separated by a llj., therefore the electrode reactions are also separated. In a galvanic cell the electrochemical reaction proceeds spontaneously. (That can be used as energy sources.) The Gibbs free energy of cell reaction is negative, r G 0 . Work is done by the system. Electrolysis cell Non-spontaneous reaction is driven by an external source of current, e.g. a battery is charged.
r G 0

Work is done on the system.

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Example galvanic cell The Daniell cell contains zinc immersed in Zn2+(aq) solution and copper immersed in Cu2+(aq) solution. The two electrodes are in galvanic contact e.g. by a salt bridge, which prevents Zn2+ and Cu2+ ions to penetrate to the other compartment causing chemical reaction. The spontaneous processes in Daniell cell when the two ion concentrations are almost the same Zn(s) Zn2+(aq) + 2eCu2+(aq) + 2e Cu(s) Zinc ions enter the aqueous phase leaving two electrons behind, so the process is oxidation and the polarity of anode is negative. Copper 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. Cell 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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If electrons flow from the left electrode (Zn/Zn2+) to the right electrode (Cu/Cu2+) 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. Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s) In the cell diagram components are marked with their phases, vertical bars simbolizes the phase boundaries. Dashed vertical line for liquid junction means that diffusion potential is not eliminated. Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s) Double vertical line for liquid junction: , means that diffusion potential has been eliminated. Cell reaction potential
zFEcell = r G

1.

Ecell, the cell reaction potential is the potential difference between electrodes, and zFEcell is the maximum work can be done by the cell. The thermodynamic sign convention for spontaneous (natural) processes: r G 0 thus Ecell 0. Ecell is measured, 1. Current approximates zero I 0 in the measuring electric circuit, so system does not do any work on surroundings. 2. diffusion potential, has been eliminated 3. cell reaction is reversible. At the conditions given Ecell is a measure of maximum work the cell could do. From the measured Ecell, knowing the cell reaction itself, the reaction Gibbs free energy can be calculated. If diffusion current should be taken into account
E MF = Ecell + d

electromotive force EMF is measured instead of Ecell. In this case a nonthermodynamic quantity is added to Ecell. In many case d can be minimized down to several milli-volts by the application of a salt bridge, and Ecell and EMF can be taken equal.

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When the cell reaction is in chemical equilibrium (at dT = 0, dp = 0)

r G = 0 and Ecell = 0

System is incapable to do any work. Cell reaction The cell reaction is the sum of half cell reactions writing in spontaneous direction. Cu2+(aq) + 2e Cu(s) Zn(s) Zn2+(aq) + 2eAdding the two processes up the result is the cell reaction. Zn + Cu2+ Cu + Zn2+ Using the sign convention the potential difference
Cu Zn = Ecell and Ecell 0

In general, the electrode placed on the right in the cell diagram should be the cathode, than subtraction
Ecell = ( Right ) ( Left )

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 consequently Ecell its sign. The proper sign can be determined by polarity measurement, by using high input resistance voltmeter. To measure EMF of a galvanic cell we use a high input resistance voltmeter. It does not load the cell, and only current in nano-Amper range flows.

The Nernst equation Reaction Gibbs free energy for cell reaction
r G = r G 0 + RT ln(Q)

2.

standard reaction Gibbs free energy Q reaction quotient

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r G 0

Dividing both sides by -zF F = 96500 C mol-1 z reaction charge number. ( z(Daniell cell) = 2))
Ecell = r G 0 RT ln(Q) zF zF

rG 0 0 , the standard cell reaction potential = Ecell zF

0 Ecell = Ecell,1

RT ln(Q ) zF

3.

For the cell reaction Zn + Cu2+ Cu + Zn2+ in Daniell cell Eq. 3. can be given,
Q= aCu a Zn , a Zn aCu
2+ 2+

for pure and homogeneous phases aCu = constant and aZn = constant, thus they are involved in standard term
0 0 Ecell = Ecell,1 +

RT a ln( Cu ) zF aZn

0 Ecell = Ecell

a 2+ RT ln( Zn ) zF aCu 2+

4.

At conditions dT = 0 and dp = 0 the Nernst equation gives the relationship between Ecell and the activity ratio of electroactive components. 0 When activity values in a galvanic cell are set as Q = 1, than Ecell = Ecell . Electrode potentials Ecell can be given as the difference of electrode potentials:
Ecell = Cu 2+ Zn 2+ = 0 + Cu 2+ RT RT ln aCu 2+ ( 0 + ln aZn 2+ ) Zn 2+ zF zF

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

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Figure 2. The electric double layer Standard cell potential At equilibrium and Q = Ka therefore
zFEcell = 0

r G = 0 ,
RT ln K a zF

0 0 = Ecell

ln K a =

0 zFEcell RT

0 The measured data for Ecell serves for the calculation of equilibrium constant.

Cell types Electrolyte concentration cell see in details, Electrode concentration cell (liquid state metal containing dissolved metal component, e. g. mercury containing copper) Electrolyte concentration cells We set a cell from two identical metal electrode (Me) and an electrolyte from a soluble salt of this metal (Me+). The Me+ activities of compartments are different, a1 and a2. Me Me+(aq), a1 Me+(aq), a2 Me

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When inequality a2 > a1 holds, Me+ in the right side electrode has a greater tendency to reduce, the spontaneous processes are: Reduction (cathodic) Me+(a2) + e Me Oxidation (anodic) Cell reaction: Nernst equation:
RT a

Me Me+(a1) + e Me+(a2) Me+(a1)

Ecell = a RT ln( 1 ) F a2

The standard cell reaction potential is zero.

1 If a1 = a2 than F ln( a ) = 0 , there is no driving force of the process, and 2 system is in chemical equilibrium: Ecell = 0. 0 =0. From Nernst equation Ecell

a1 <1 a2

ln

a1 <0 a2

and Ecell > 0 as it should be. Metal metal-ion electrode Example: Ag(s)/AgNO3 electrode The electrochemical process which determines the electrode potential Ag+ + e- Ag The activity dependence of electrode potential (Nernst equation)
a Ag RT RT a Ag + 0 0 Ag = Ag ln = Ag + ln F a Ag + F a Ag

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

RT 0 Ag = Ag + ln a Ag + F

At constant temperature electrode potential depends on the silver ion activity. Metal insoluble salt electrodes Composition: solid or liquid metal e.g. Hg,
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an insoluble salt of metal e.g. Hg2Cl2, a c concentration electrolyte of well soluble salt of the anion e.g. KCl. Often, the metal is covered by its insoluble salt. The electrochemical process which determines the electrode potential of calomel electrode (Hg(s)Hg2Cl2(s) c(KCl)aq) Hg2Cl2 + 2e = 2Hg + 2 ClThe concentration dependence of electrode potential (Nernst equation) for calomel electrode,
2 2 RT aCl a Hg 0 cal = cal ln 2 F a Hg 2 Cl 2

where the activity of solid Hg and Hg2Cl2phases are unity, thus

0 cal = cal

RT ln a Cl F

Metal insoluble salt electrodes are used as reference electrodes because they can not be polarized easily. A current flowing through the electrode causes no change in activity of electroactive components. The solubility equilibrium of insoluble salt of metal stabilizes activities. E.g. for Ag/AgCl/KCl electrode the value of solubility product constant, Ksp=[Ag+][Cl-]=1.8 x 10-10. The chloride activity is maintained either by dissolution or deposition of AgCl when polarization would consume or produce excess amount of Ag+ ions.

Ion ion (redox) electrode A single liquid phase contains both the oxidized and reduced forms of electrode reaction. A noble metal electrode, e.g. Pt senses the potential difference between the bulk of solution and the metal. The electron exchange occurs in the liquid phase. The electrochemical process which determines the electrode potential of redox electrode Pt(s)cFe2+(aq), cFe3+(aq) Fe3+ + e = Fe2+

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0 Fe 2+ / Fe3+ = Fe 2+ / Fe3+

RT aFe 2+ ln F aa 3 +
Fe

If

a ( Fe 3+ ) =1 a ( Fe 2+ )

RT a ( Fe 3+ ) ln( ) =0 zF a ( Fe 2+ )

The electrode potential is identical to the standard potential.

0 Fe 2 + / Fe3+ = Fe 2+ / Fe3+ 0 Fe = +0.771 2+ / Fe 3+

V at T = 293 K.
RT a ( Fe 3 + ) ln( ) <0 zF a ( Fe 2 + )

If

a ( Fe

3+

a ( Fe 2 + )

<1

The electrode potential is less than the standard potential.

0 Fe 2 + / Fe3+ Fe 2+ / Fe3+

The hydrogen gas electrode Some electrode reactions involve a gaseous species such as H2, O2, or Cl2. Such reactions must also be carried out on the surface of an electrochemically inert conductor such as platinum.

Figure 4. Hydrogen gas for saturating the acidic solution. The half cell contains a liquid phase of hydrogen gas saturated acidic solution, a solid phase of platinized platinum electrode having high surface area,

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and a gas phase of a pH 2 pressure hydrogen gas in equilibrium with the dissolved hydrogen. The high catalytic surface of Pt catalyses the reaction H2 2Hads and the electrode reaction between the adsorbed hydrogen atoms and hydrogen ions in solution occurs. Half cell reaction or electrode reaction H+ + 2e- = 1/2H2 The electrode potential: The Nernst equation
= M s
0 H =H

RT 1 ln 2 2F a +
H

pH 2 p0

The Nernst equation represents that the electrode potential of a hydrogen gas electrode depends on the activity of H+ and the pressure of H2 gas at constant temperature. The electrochemical potential scale The reference point of potential scale: the standard hydrogen electrode. If the pressure of H2 over the liquid is the standard pressure p H 2 = p 0 = 1 bar , we have
H = 0 H RT 1 ln F aH +

Standard hydrogen electrode, the zero point of electrochemical potential scale When the activity of hydrogen ions is the unity,
H = 0 H
0 and this standard electrode potential of hydrogen electrode H was chosen as zero Volt for each temperature value.

The measurement of pH Cell setup: A second order reference half cell (ion insoluble salt metal) is attached to a hydrogen electrode.
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Figure 5. The saturated calomel electrode. When saturated solution of KCl is used as electrolyte its electrode potential: 0.24 V at 293 K vs. SHE. The half cell reaction of HE 2H+ + 2e = H2 Cell reaction 2H+ + 2Cl- + 2 Hg = Hg2Cl2 + H2 Cell diagram: Hg Hg2Cl2(s) satd. KCl sol. cH+ H2 gas Pt Nernst equation:
0 E MF = E MF

p H / p0 a Hg a Hg Cl RT ln 2F a 2 H + a 2 Cl
2

( ) ( )

aHg = 1, aHg2Cl2 = 1 p0 = pH2 = 1 bar

solid phases

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0 E MF = E MF +

RT ln a H + a Cl F

( ) (

) ( )

0 E MF = E MF ln 10

RT pH + ln a Cl F

0 0 0 0 = H cal = cal The standard cell reaction potential: EMF

E MF = cal ln10

RT pH F

For reduction of problems with liquid junction and unknown activities we use reference standard pH electrodes. The same platinized platinum is immersed into both solutions, and joined to the same secondary reference electrode. Cell with unknown pH
Eu = cal ln10 RT pH u F

Cell with reference standard (UPAC recommended) pH

E r = cal ln10 RT pH r F

The difference between the two measured electromotive force

Eu Er = ln10 RT RT pH u + ln10 pH r F F

The unknown pH can be given finally

pH u = pH r Eu E r RT ln10 F

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TABLE for standard electrode (reduction) potentials at T = 298 K, referred to SHE Half reaction standard electrode potential / V F2 + 2e = 2F 2.866 + Au + e = Au 1.692 Cl2 + 2e = 2Cl 1.358 + Ag + e = Ag 0.799 2+ Hg 2 + 2e = 2Hg 0.851 2+ Cu + 2e = Cu 0.342 + 2H + 2e = H2 0. 0 by definition 2+ Zn + 2e = Zn -0.762 + Li + e = Li -3.040 The standard cell reaction potential of Daniell cell is taken from table,
0 0 E 0 = Cu Zn = 0.342 ( 0.762) = 1.104 V

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Figure 6. The structure of glass membrane electrode. The electrode reaction potential With the SHE 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. 2. Ag+ + e = Ag H+ + e = 1/2H2 Ag+ + 1/2H2 = Ag + H+ ,
H = 0

1. - 2.:
Ecell = Ag H
0 Ecell = Ag

RT 1 ln F a Ag

When aAg = 1,
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0 Ecell = Ag

referred to the SHE.

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Applying the activity concentration relation,

0 Ecell = Ag +

RT c Ag ln 0 F c

0 Ecell = Ag +

RT RT c Ag ln + ln 0 F F c
RT c Ag ln 0 F c

Ecell = 0 f +

where 0 f is the formal potential. Temperature dependence of Ecell, EMF

r G = r H T r S
r G = r S T p

G rG = r H + T r T
r G = zFE MF

E zFE MF = r H zFT MF T

E MF =

1 E r H T MF zF T

E r H = zF E MF T MF T
r S = rG r H + T T

Gibbs Helmholtz equation. The reaction entropy can be calculated.

Membrane equilibrium, electrochemical potential.

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Figure 8. Membrane selectively permeable to water and SO 2 4

Processes, cathode: anode membrane Overall process:

2+ Cu2+ + Zn + SO 2 + SO 2 4 (R) Cu + Zn 4 (L)

Cu2+ + 2e- = Cu Zn2+ + 2e- = Zn 2SO 2 4 ( R ) SO 4 ( L )

a( SO 4 , R ) > a( SO 4 , L )

The reaction Gibbs free energy for the overall reaction,

r GT , p = i i
i

r GT , p = Cu + Zn + SO ( L ) Cu Zn SO ( R )
2+ 4 2+ 4

The chemical potential of components take part in the process

0 0 Cu = Cu + RT ln a( Cu ) = Cu

0 Zn = Zn

0 Zn = Zn + RT ln a Zn 2+
2+ 2+

0 Cu = Cu + RT ln a Cu 2+
2+ 2+

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0 SO = SO + RT ln a SO 2 4 ,L
4 4

0 SO = SO + RT ln a SO 2 4 ,R
4 4

)
( ) ( )

The reaction Gibbs free energy given by activities

0 0 0 2 0 r GT , p = Cu + Zn + RT ln a Zn 2+ + SO + RT ln a SO4 , L Cu RT ln Cu 2+
2+

0 0 2 Zn SO RT ln a SO4
4

( , R)

2+

0 0 0 0 r GT , p = Cu + Zn Cu Zn + RT ln
2+ 2+

2 a Zn 2+ a SO4 ,L 2+ 2 a Cu a SO4 , R

( (

)( )(

) )

The sum of standard chemical potentials equals to the standard reaction Gibbs free energy
0 r GT , p = r GT , p + RT ln 2 a Zn 2+ a SO4 ,L 2+ 2 a Cu a SO4 , R

( (

)( )(

) )

Now, we introduce the measured potential difference:

E = Cu Zn = r G / 2 F
2 ,R RT a Cu 2+ RT a SO4 E , = E 0+ ln + ln 2 F a Zn 2+ 2 F a SO 2 , L 4 membrn

( (

) )

( (

) )

membrn

The first two terms are identical to the electromotive force of a Daniell cell with a salt bridge without membrane potential.
E = = Cu Zn
S membrn = R S L 2 ,R RT a SO4 = ln 2 2 F a SO4 , L

( (

) )

Rearranging the last equation and adding standard chemical potential to both sides, we get
0 2 S 0 2 S SO + RT ln a SO4 , L 2 F L = SO + RT ln a SO4 , R 2 F R 4 4

Introducing electrochemical potential: = + zF

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 SO4 ( R ) = SO4 ( L )

When regions of different electric potentials present, there is an additive condition of equilibrium: electrochemical potential of charged species i must be the same in every phase. Generalization For dilute solutions activities can be replaced by concentrations, c
0 + RT ln c1 zF1 = 0 + RT ln c2 zF2

divided by NA
kT ln
c2 c = ze(2 1 ) 2 = e c1 c1 ze kT

Boltzmann distribution. Redox reaction involves the participation of H+ The fumarate (FUM2-) to succinate (SUC2-) reduction Half reaction: OOC CH = CH COO + 2H + + 2e OOC CH 2 CH 2 COO Electrons are taken from the bonding Cell reaction: the redox half cell is coupled to a SHE SHE FUM2-,SUC2-,H+(a2) Pt Half reaction on the left: Overall reaction:
0 EMF = E MF

2H+ + 2e = H2 FUM2- + 2H+(a2) = SUC2- + H+(a1)

RT a( SUC 2 ) a12 ( H + ) p 0 ln 2 F a12 ( H + ) a( FUM 2 ) p H

In standard hydrogen electrode: a1 = 1, pH2 = p0 = 1 bar

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RT a( SUC 2 ) E MF = E ln 2 F a12 ( H + ) a( FUM 2 )

0 MF

The organic redox process is pH dependent. The pH definition:

ln ( a ( H + ) ) = ln 10 lg( a ( H + ) ) pH ln ( a 2 ( H + ) ) = 2 ln10 lg( a ( H + ) ) 2 pH

RT 2 + RT a ( SUC 2 ) EMF = E + ln a1 ( H ) + ln 2F 2 F a( FUM 2 )

0 MF

RT 2 + RT a ( SUC 2 ) EMF = E + ln a1 ( H ) + ln 2F 2 F a( FUM 2 )

0 MF

Substituting pH

RT RT a( SUC 2 ) EMF = E ln10 pH + ln F 2 F a( FUM 2 )

0 MF

The value of constant

8.314 J/(molK), it is 0.05911 V. On increasing the pH by one the electromotive force of the cell will decrease by 59 mV.

RT ln 10 F

is given at T = 298 K, F = 96500 C/mol, R =

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