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Equilibrium Electrochemistry, Chapter 3(pp.

119 120) & Chapter 6 General Objective Description of properties of solutions of electrolytes; Thermodynamic properties of reactions that take place in electrochemical cells; Electric potential of cells; Definition and tabulation of standard potentials; Use of standard potentials to determine equilibrium constants and thermodynamic properties of chemical reactions. Thermodynamic Functions of Formation of Ions in Solutions Standard functions of formation of ions Values of fH and fG refer to the formation of solutions of ions from the reference states of the parent elements Complication: Cations cannot be separated from anions Ag(s) + Cl2(g) Ag+(aq) + Cl(aq) fH = fH(Ag+, aq) + fH(Cl, aq) = 61.58 kJ mol1

CHEM 221, Lecture 4-1 Equilibrium Electrochemistry

Important: Enthalpies of individual ions are not measurable Convention: Enthalpy and Gibbs energy of formation of the hydrogen ion (hydronium cation) is zero at all temperatures f H o (H + , aq) = 0 f G o (H + , aq) = 0

This definition adjusts the value of one ion determination of enthalpies and Gibbs energies of other ions Example H2 + Cl2 H+(aq) + Cl(aq) rG = 131.23 kJ mol1

rG = fG(H+, aq) + fG(Cl, aq) fG(Cl, aq) = 131.23 kJ mol1 Example: Calculate fG(Ag+, aq) knowing that rG of the following reaction: Ag(s) + Cl2 Ag+(aq) + Cl(aq) rG = 54.12 kJ mol1

fG(Ag+, aq) = 54.12 (131.23) = 77.11 kJ mol1


CHEM 221, Lecture 4-1 Equilibrium Electrochemistry
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Contributions to the Gibbs energy of formation of ions Analysis of a thermodynamic cycle for reaction: H2(g) + Cl2(g) H+(aq) + Cl(aq) fG(H+, aq) + fG(Cl, aq) = = 1272 kJ mol1 + solvG(H+, aq) + solvG(Cl, aq)

Observation: fG of an ion Cl includes contributions from dissociation, ionization, electron gain and hydration Gibbs energies of solvation of individual ions electrical work (non-expansion work) of transferring an ion from a vacuum (o) to the solution ( = r o): Electric potential () of a sphere (radius, ri) having charge q: = q 4 ri
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CHEM 221, Lecture 4-1 Equilibrium Electrochemistry

Work of bringing charge dq to the sphere in a vacuum:


1 w = dq = 4 o ri 0
zie zie

z i2 e 2 q dq = 8 o ri

zi charge number of the ion Work of bringing charge dq to the sphere in a continuous dielectric medium of r:
z i2 e 2 w= 8 o r ri

solvG = w(medium) w(vacuum) Born equation z i2 e 2 N A 1 1 solv G = 8 o ri r


o

Observations: (i) solvG < 0; (ii) solvG strongly negative for small, highly charged ions in media of high r

CHEM 221, Lecture 4-1 Equilibrium Electrochemistry

For water:

z i2 solv G = 6.86 10 4 kJ mol 1 (ri / pm)


o

Example Estimate the value of solvG for F and K+ in water at T = 298 K; the ionic radii are 133 and 138 pm, respectively. solvG(F, aq) = 515 kJ mol1 solvG(K+, aq) = 497 kJ mol1 Standard entropies of ions in solution Partial molar entropy of the solute in an electrolyte solution can be measured We are unable to ascribe a part of the entropy to cations and anions Convention: entropies of ions in solutions are reported with respect to the standard entropy of H+ in water So (H + , aq) = 0
CHEM 221, Lecture 4-1 Equilibrium Electrochemistry

at all temperatures
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Interpretation: partial molar entropies of ions can be related to the degree of organization of water molecules around them (a) positive entropy smaller degree of organization of water molecules than H+(aq) (b) negative entropy greater degree of organization of water molecules than H+(aq) Table: Standard entropies of ions in aqueous solutions at 298 K Small, highly charged ions: induce local structure in the surrounding water Large, singly charged ions disorder the structure

CHEM 221, Lecture 4-1 Equilibrium Electrochemistry