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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: “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)+2e→Cu(s) containing its own ions. Noble metal in contact Fe3+(aq)+e→Fe2+(aq) with solution of a redox couple Metal in contact with its Hg2Cl2(s)+2e→2Hg+2Clinsoluble salt (i.s.) and a solution containing a soluble anion of the i.s. Noble metal in contact H+(aq)+e→1/2H2(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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Cell diagram is constructed to show the cell reaction running in spontaneous direction. the positive ion drifts from left to right. by a salt bridge. so the process is reduction polarity of cathode is positive. which prevents Zn2+ and Cu2+ ions to penetrate to the other compartment causing chemical reaction. sign convention The cell diagram involves instructions for setting the cell and should be in conform with the cell reaction. so the process is oxidation and the polarity of anode is negative. 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.Example galvanic cell The Daniell cell contains zinc immersed in Zn2+(aq) solution and copper immersed in Cu2+(aq) solution. i. Ecell should always be positive.g. L02Elchem 3 .e. The two electrodes are in galvanic contact e. Copper ions deposit to the copper taking up two electrons from metal. The cell diagram. The sign of cell reaction potential.

means that diffusion potential has been eliminated. the cell reaction potential is the potential difference between electrodes. In many case ϕ d can be minimized down to several milli-volts by the application of a salt bridge. At the conditions given Ecell is a measure of maximum work the cell could do. Zn(s) │ ZnSO4(aq) ¦ CuSO4(aq) │ Cu(s) In the cell diagram components are marked with their phases. vertical bars simbolizes the phase boundaries. The thermodynamic sign convention for spontaneous (natural) processes: ∆r G ≤ 0 thus Ecell ≥ 0. cell reaction is reversible. L02Elchem 4 . Cell reaction potential − zFEcell = ∆ r G 1. so system does not do any work on surroundings. From the measured Ecell. and Ecell and EMF can be taken equal. Zn(s) │ ZnSO4(aq) ║ CuSO4(aq) │ Cu(s) Double vertical line for liquid junction: ║.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. In this case a nonthermodynamic quantity is added to Ecell. the reaction Gibbs free energy can be calculated. If diffusion current should be taken into account E MF = Ecell + ϕ d electromotive force EMF is measured instead of Ecell. and zFEcell is the maximum work can be done by the cell. knowing the cell reaction itself. φ has been eliminated • 3. • 1. the potential of electrode on the right will be higher than that of the left. Ecell is measured. Dashed vertical line ¦ for liquid junction means that diffusion potential is not eliminated. • 2. diffusion potential. Current approximates zero I → 0 in the measuring electric circuit. Ecell.

than subtraction Ecell = ϕ ( Right ) − ϕ ( Left ) will give positive result. To measure EMF of a galvanic cell we use a high input resistance voltmeter. dp = 0) ∆ r G = 0 and Ecell = 0 System is incapable to do any work. and only current in nano-Amper range flows. The cell reaction can change its direction and consequently Ecell its sign. by using high input resistance voltmeter.When the cell reaction is in chemical equilibrium (at dT = 0. standard reaction Gibbs free energy Q reaction quotient L02Elchem 5 ∆r G 0 . The proper sign can be determined by polarity measurement. the electrode placed on the right in the cell diagram should be the cathode. Cu2+(aq) + 2e → Cu(s) Zn(s) → Zn2+(aq) + 2eAdding the two processes up the result is the cell reaction. The Nernst equation Reaction Gibbs free energy for cell reaction ∆r G = ∆r G 0 + RT ln(Q) 2. Cell reaction The cell reaction is the sum of half cell reactions writing in spontaneous direction. The real spontaneous direction depends on the actual concentration/activity values in the cell. Zn + Cu2+ → Cu + Zn2+ Using the sign convention the potential difference ϕCu − ϕZn = Ecell and Ecell ≥ 0 In general. It does not load the cell.

Q= aCu a Zn . L02Elchem 6 . At conditions dT = 0 and dp = 0 the Nernst equation gives the relationship between Ecell and the activity ratio of electroactive components. than Ecell = Ecell .Dividing both sides by -zF F = 96500 C mol-1 z reaction charge number. a Zn aCu 2+ 2+ for pure and homogeneous phases aCu = constant and aZn = constant. owing to formation of double layer at the interface. thus they are involved in standard term 0 0 Ecell = Ecell. For the cell reaction Zn + Cu2+ → Cu + Zn2+ in Daniell cell Eq. can be given. the standard cell reaction potential = Ecell zF 0 Ecell = Ecell. 0 When activity values in a galvanic cell are set as Q = 1. Electrode potentials Ecell can be given as the difference of electrode potentials: Ecell = εCu 2+ − ε Zn 2+ = ε0 + Cu 2+ RT RT ln aCu 2+ − ( ε0 + ln aZn 2+ ) Zn 2+ zF zF Electrode potential is the difference between potential in the metal and the bulk of solution.1 + RT a ln( Cu ) zF aZn 0 Ecell = Ecell − a 2+ RT ln( Zn ) zF aCu 2+ 4. Individual electrode potentials can not be measured. ( z(Daniell cell) = 2)) Ecell = − ∆ r G 0 RT − ln(Q) zF zF − ∆rG 0 0 . 3.1 − RT ln(Q ) zF 3.

Me │ Me+(aq). a1 and a2. a2 │ Me L02Elchem 7 . The electric double layer Standard cell potential At equilibrium and Q = Ka therefore − zFEcell = 0 ∆r G = 0 . • Electrode concentration cell (liquid state metal containing dissolved metal component. 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. e. 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+). g. The Me+ activities of compartments are different.Figure 2. a1 ║ Me+(aq).

Metal metal-ion electrode Example: Ag(s)/AgNO3 electrode The electrochemical process which determines the electrode potential Ag+ + e.When inequality a2 > a1 holds. and 2 system is in chemical equilibrium: Ecell = 0.→ Ag The activity dependence of electrode potential (Nernst equation) a Ag RT RT a Ag + 0 0 ε Ag = ε Ag − ln = ε Ag + ln F a Ag + F a Ag where the activity of a single component solid Ag phase is unity. Metal insoluble salt electrodes Composition: solid or liquid metal e. there is no driving force of the process. thus RT 0 ε Ag = ε Ag + ln a Ag + F At constant temperature electrode potential depends on the silver ion activity. 0 =0.g. 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. Hg. L02Elchem 8 . From Nernst equation Ecell a1 <1 → a2 ln a1 <0 a2 and Ecell > 0 as it should be. 1 If a1 = a2 than − F ln( a ) = 0 .

thus 0 ε cal = ε cal − RT ln a − Cl F Metal insoluble salt electrodes are used as reference electrodes because they can not be polarized easily.g. KCl. cFe3+(aq) Fe3+ + e = Fe2+ L02Elchem 9 . A noble metal electrode. The solubility equilibrium of insoluble salt of metal stabilizes activities. e. Ion – ion (redox) electrode A single liquid phase contains both the oxidized and reduced forms of electrode reaction.an insoluble salt of metal e. Often.g. The chloride activity is maintained either by dissolution or deposition of AgCl when polarization would consume or produce excess amount of Ag+ ions. E. Hg2Cl2.g. Ksp=[Ag+][Cl-]=1. The electrochemical process which determines the electrode potential of redox electrode Pt(s)│cFe2+(aq). Pt senses the potential difference between the bulk of solution and the metal. for Ag/AgCl/KCl electrode the value of solubility product constant.g. a c concentration electrolyte of well soluble salt of the anion e.8 x 10-10. the metal is covered by its insoluble salt. The electron exchange occurs in the liquid phase. 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. A current flowing through the electrode causes no change in activity of electroactive components. 2 2 RT aCl − a Hg 0 ε cal = ε cal − ln 2 F a Hg 2 Cl 2 where the activity of solid Hg and Hg2Cl2phases are unity.

Such reactions must also be carried out on the surface of an electrochemically inert conductor such as platinum.0 ε Fe 2+ / Fe3+ = ε 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. O2. Figure 4. 0 ε Fe 2 + / Fe3+ = ε Fe 2+ / Fe3+ 0 εFe = +0. 0 ε Fe 2 + / Fe3+ ≤ ε Fe 2+ / Fe3+ The hydrogen gas electrode Some electrode reactions involve a gaseous species such as H2. Hydrogen gas for saturating the acidic solution. 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.771 2+ / Fe 3+ V at T = 293 K. L02Elchem 10 . a solid phase of platinized platinum electrode having high surface area. The half cell contains a liquid phase of hydrogen gas saturated acidic solution. or Cl2.

εH = ε0 H 0 and this standard electrode potential of hydrogen electrode εH was chosen as zero Volt for each temperature value.= 1/2H2 The electrode potential: The Nernst equation ε = ϕM − ϕs 0 εH =εH − 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. If the pressure of H2 over the liquid is the standard pressure p H 2 = p 0 = 1 bar . Half cell reaction or electrode reaction H+ + 2e. 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. The measurement of pH Cell setup: A second order reference half cell (ion │insoluble salt │metal) is attached to a hydrogen electrode. The electrochemical potential scale The reference point of potential scale: the standard hydrogen electrode. L02Elchem 11 . we have εH = ε0 H − RT 1 ln F aH + Standard hydrogen electrode.and a gas phase of a pH 2 pressure hydrogen gas in equilibrium with the dissolved hydrogen. the zero point of electrochemical potential scale When the activity of hydrogen ions is the unity.

aHg2Cl2 = 1 p0 = pH2 = 1 bar solid phases L02Elchem 12 . SHE. The saturated calomel electrode.24 V at 293 K vs. ║ 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 ( ( ) ( ) ) 2 2 aHg = 1.Figure 5. KCl sol. The half cell reaction of HE 2H+ + 2e = H2 Cell reaction 2H+ + 2Cl. When saturated solution of KCl is used as electrolyte its electrode potential: 0.+ 2 Hg = Hg2Cl2 + H2 Cell diagram: Hg │ Hg2Cl2(s) │ satd.

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 = εH − ε cal = −ε cal The standard cell reaction potential: EMF E MF = −ε 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 = −ε cal − ln10 ⋅ RT pH u F Cell with reference standard (UPAC recommended) pH E r = −ε 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 L02Elchem 13 .

referred to SHE Half reaction standard electrode potential / V F2 + 2e = 2F 2.762 + Li + e = Li -3.851 2+ Cu + 2e = Cu 0.866 + Au + e = Au 1.342 + 2H + 2e = H2 0.040 The standard cell reaction potential of Daniell cell is taken from table.104 V L02Elchem 14 . 0 0 E 0 = ε Cu − ε Zn = 0.342 − ( −0.358 + Ag + e = Ag 0. 0 by definition 2+ Zn + 2e = Zn -0.692 Cl2 + 2e = 2Cl 1.TABLE for standard electrode (reduction) potentials at T = 298 K.799 2+ Hg 2 + 2e = 2Hg 0.762) = 1.

: Ecell = ε Ag − ε H 0 Ecell = ε Ag − RT 1 ln F a Ag When aAg = 1.2. 2. 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. εH = 0 1.Figure 6. The structure of glass membrane electrode. Ag+ + e = Ag H+ + e = 1/2H2 Ag+ + 1/2H2 = Ag + H+ . 15 . L02Elchem → 0 Ecell = ε Ag referred to the SHE. .

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. electrochemical potential. Temperature dependence of Ecell. 0 Ecell = ε Ag + RT γ ± c Ag ln 0 F c 0 Ecell = ε Ag + RT RT c Ag ln γ ± + ln 0 F F c RT c Ag ln 0 F c Ecell = ε 0 f + where ε0 f is the formal potential. Membrane equilibrium.Applying the activity concentration relation. L02Elchem 16 . The reaction entropy can be calculated.

R ) > a( SO 4 .= Zn 2SO 2 4 ( R ) → SO 4 ( L ) a( SO 4 .= Cu Zn2+ + 2e. p = ∑ν i µi i ∆ r GT .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. L ) The reaction Gibbs free energy for the overall reaction. p = µ Cu + µ Zn + µ SO ( L ) − µ Cu − µ Zn − µ SO ( R ) 2+ 4 2+ 4 The chemical potential of components take part in the process 0 0 µCu = µCu + RT ln a( Cu ) = µCu 0 µZn = µZn 0 µ Zn = µ Zn + RT ln a Zn 2+ 2+ 2+ ( ) 0 µ Cu = µ Cu + RT ln a Cu 2+ 2+ 2+ ( ) L02Elchem 17 . ∆r GT .

L − µ Cu − RT ln Cu 2+ − 2+ 0 0 2− − µ Zn − µ SO − RT ln a SO4 4 ( ( . p = µ Cu + µ Zn + RT ln a Zn 2+ + µ SO + RT ln a SO4 . R − 2 Fϕ R 4 4 ( ) ( ) Introducing electrochemical potential: µ = µ + zFϕ L02Elchem 18 .L 4 4 ( ) 0 µ SO = µ SO + RT ln a SO 2 4 . L            4 ∆ϕ −ϕ membrán ( ( ) ) ( ( ) ) ϕ membrán The first two terms are identical to the electromotive force of a Daniell cell with a salt bridge without membrane potential. we introduce the measured potential difference: E = ϕCu − ϕ Zn = −∆ r G / 2 F 2− .L 2+ 2− a Cu a SO4 . p = ∆ r GT . p + RT ln 2− a Zn 2+ a SO4 . = E 0+ ln + ln 2 F a Zn 2+ 2 F a SO 2− . we get 0 2− S 0 2− S µ SO + RT ln a SO4 .R 4 4 ( ) ( ) ( ) The reaction Gibbs free energy given by activities 0 0 0 2− 0 ∆ r GT .R RT a Cu 2+ RT a SO4 E . p = µ Cu + µ Zn − µ Cu − µ Zn + RT ln 2+ 2+ 2− a Zn 2+ a SO4 .R RT a SO4 = ln 2− 2 F 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 . L − 2 Fϕ L = µ SO + RT ln a SO4 . R ( ( )( )( ) ) Now. E = ∆ϕ = ϕ Cu − ϕ Zn S ϕ membrán = ϕ R S − ϕL 2− .0 µ SO = µ SO + RT ln a SO 2 4 . L ( ( ) ) Rearranging the last equation and adding standard chemical potential to both sides. R) ) 4 2+ 0 0 0 0 ∆ r GT .

c µ 0 + RT ln c1 − zFϕ1 = µ 0 + RT ln c2 − zFϕ2 divided by NA − kT ⋅ ln − c2 c = ze(ϕ2 − ϕ1 ) ⇒ 2 = e c1 c1 ze∆ϕ kT Boltzmann distribution.SUC2-. Generalization For dilute solutions activities can be replaced by concentrations. 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 π bonding Cell reaction: the redox half cell is coupled to a SHE SHE ║ FUM2-.µ SO4 ( R ) = µ 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.+ H+(a1) RT a( SUC 2− ) ⋅ a12 ( H + ) ⋅ p 0 ln 2 F a12 ( H + ) ⋅ a( FUM 2− ) ⋅ p H 2 In standard hydrogen electrode: a1 = 1. pH2 = p0 = 1 bar L02Elchem 19 .+ 2H+(a2) = SUC2.H+(a2) │ Pt Half reaction on the left: Overall reaction: 0 EMF = E MF − 2H+ + 2e = H2 FUM2.

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. RT ln 10 F is given at T = 298 K.314 J/(molK).05911 V. F = 96500 C/mol. R = L02Elchem 20 . On increasing the pH by one the electromotive force of the cell will decrease by ≈ 59 mV. it is 0.