EQUILIBRIUM

ELECTROCHEMISTRY
 equilibrium electrochemistry
 discussion:

- equilibria of reaction in terms of the electrode potential

- electrochemical measurements
 Gibbs functions, enthalpies, and entropies of reactions

- applications in typical chemical problems

 Keq, Ka, Kb
= examine information  from potential difference between
two electrodes
……. firstly, look into the properties of ions in solution
equilibrium electrochemistry
 Chemical Equilibrium

- concept of chemical potential

- concept of Gibbs function or Gibbs free energy

thermodynamic properties of electrolyte
solutions
= well discussed in terms of chemical
potentials and activities in the same way
as non-electrolytes
 equilibrium electrochemistry
 two (2) distinct features:

(1) strong interaction between ions in solutions

 activity coefficients that differ from 1

(2) reactions involving ions and electrons exchange

 electrochemical cells

characteristics of electrolyte solutions and
ionic equilibrium
 equilibrium electrochemistry
 Thermodynamic Functions of Formation
= the thermodynamic function of a reaction
rHo  fHo rGo  fGo
= for ions -
A(s) + B(s)  A+(aq) + B(aq)
rHo = fHo(A+(aq)) + fHo(B(aq))
rGo = fGo(A+(aq)) + fGo(B(aq))
* enthalpy of an overall reaction
= is meaningful and measurable
equilibrium electrochemistry

A(s)  A+(aq) + e

B(s) + e  B(aq)

* ionic equations - enthalpies not measurable

 equilibrium electrochemistry
 to make problem simpler :

@ define one ion to have zero value for its

thermodynamic property of formation

* thus, ion = H+(aq)  fHo(H+(aq)) = 0 )

fGo(H+(aq)) = 0 )
- at all temperatures

@ no way of distributing part of the entropy to

cation or anion
fSo(H+(aq)) = 0 , at all temperatures
 equilibrium electrochemistry
 contribution of the Gibbs energy of formation:
example:
½ H2(g) + ½ X2(g or l)  H+(aq) + X(aq)

Gibbs energy comes from:

(1) dissociation of H2 (4) formation of X
(2) ionization of H (5) electron gain by X
(3) hydration of H+ (6) hydration of X

= the sum of the above will give = fGo(X(aq))

 equilibrium electrochemistry
 Gibbs energies of hydration hydGo
= Gibbs energies of solvation solvGo

 estimated by Born equation:

2
z e
2
N A 1
 solv G  1 
o i

8o ri  r 
electrochemistry
Electrochemical Cells
= electrical measurements
= basic apparatus : @ electrochemical cell
@ two electrodes
@ electrolyte
= electrode compartment
- may share same compartment
- different compartment - with salt bridge
 electrochemistry
 Two principal types of electrochemical cell -
(1) Galvanic Cell (or Voltaic)
(2) Electrolytic Cell

 Redox reactions  transfer of electrons

= reducing agent (reductant) = electron donor
= oxidizing agent (oxidant) = electron acceptor
 electrochemistry
 Half - reactions
= reactions showing the loss and gain of electrons
 Redox couple
= oxidized and reduced substance in a half reaction
ex. Cu2+/Cu or Zn2+/Zn  in general Ox/Red
 Reactions at electrodes
- electrochemical cell
 oxidation/reduction processes
- one half reaction takes place in one electrode
electrochemistry
Reactions:
@ oxidation  anode

Anode reaction: Red1  Ox1 + ne

@ reduction  cathode

Cathode reaction: Ox2 + ne  Red2

 electrochemistry
Varieties of electrodes
@ metal/metal ion electrode
ex. Cu in aq. Cu2+
denoted: MM+(aq)  CuCu2+(aq)
@ gas electrode
ex. H2 electrode
PtH2(g)H+(aq)
@ metal/insoluble-salt electrode
MMX(s)X
rxn: MX(s) + e  M(s) + X(aq)
electrochemistry
another way of classifying cells

(1) chemical cells

- chemical reaction

(2) concentration cells

- concentration changes
electrochemistry
H2(g, pH2)HCl(aq, aHCl),AgCl(s)Ag ZnZn2+Cd2+Cd
 electrochemistry
Cell A : cell without liquid junction
H2(g, pH2)HCl(aq, aHCl),AgCl(s)Ag
Cell B : cell with liquid junction
ZnZn2+Cd2+Cd
@ similarly, for concentration cell
 with or without liquid junction (LJ)
 different electrolyte or concentration
 common electrolyte, different concentration
 electrochemistry
Liquid Junction Potential
= with compartments - porous membrane or salt
bridge
= LJ potential results:
- two solutions of different concentration or
different ions
- arises from diffusion of ions across the
boundary
= concentration gradient exists across the boundary
 electrochemistry
@ examples
(1) water poured over concentrated HCl or
concentrated H2SO4

(2) membrane in a cell

 ions of unequal velocity - diffuses differently
= results in the separation of charges
 causing the establishment of a potential

= liquid junction potential

thus:
Ecell = E1 + E2 + ELJ
 electrochemistry
 ELJ = cannot be measured experimentally

= calculated = attempted by several researches

 best way = remedy = minimize or reduce

 using a salt bridge

 electrochemistry
Cell Representation
= use of formulas and vertical bars
* Given the cell : ZnZn2+(a = 1)Cd2+(a = 1)Cd

* By convention:
- left side = () = negative electrode
= oxidation  anode
- right side = (+) = positive electrode
= reduction  cathode
- electron flow = from left to right
 electrochemistry
 half reactions:
- Anode: Zn(s) = Zn2+(a = 1) + 2e EZn

- Cathode: Cd2+(a = 1) + 2e = Cd(s) ECd

- overall cell reaction

Zn(s) + Cd2+(a = 1) = Zn2+(a = 1) + Cd(s) Ecell
and,
Ecell = EZn + ECd
 electrochemistry
Reversibility and spontaneity of reactions

= a cell reaction that has not reached chemical

equilibrium
 can do electrical work

= a reaction yields a potential E and supplies a

quantity of electricity

E = zero-current potential  cell = reversible

electrochemistry
= electrical work of the reaction = nFE
* when electrical work is maximum
 a cell operates reversibly
* when performed by a cell
= only by decrease in free energy
 decrease in free energy, G
= maximum work
thus,
G = nFE at std. state G = nFE
 electrochemistry
 the reversible E, zero-current potential
= determined by the free energy change

 “bridge” between thermodynamics and

electrochemistry
for spontaneous reaction:
G = ()  E = (+)
non-spontaneous reaction:
G = (+)  E = ()
equilibrium: G = 0  E = 0
 electrochemistry
 relationship of zero-current cell potential (E) to
activities of components in the cell for the reaction:
A + B = C + D
a C aD
* Gibbs energy relationship : r G  r G  RTln
o

aA aB
Q a C aD
= reaction quotient
aA aB
 rG  rG
o
RT
- dividing by nF:    lnQ
nF nF nF

- simplifying,  rG RT
o

E  lnQ
nF nF
electrochemistry
since, G = nFE then,
RT
E  E  lnQ
o

nF
 Nernst Equation

= for the zero-current cell potential at any cell

composition

@ reaction at equilibrium :
G = 0, E = 0, and Q = K
RT nFE
o

E  lnK or lnK 
o

nF RT
 electrochemistry
 other thermodynamic properties

- the cell potential is related to the reaction Gibbs

energy
G = nFE
What about the change in enthalpy?

- differentiating with respect to T,

  G  nF  E 
 T P  T P

- from the Gibbs-Helmholtz equation

    G 
G  H  T 
 T P
 electrochemistry
 substituting equations,
 E 
 nFE  H  nFT  
 T P
- solving for H,
  E  
H  nF T    E
  T P 
 E 
  = temperature coefficient of the potential E
 T P

or
 E 
ΔG  H  nFT  
 T P
electrochemistry

 E 
= so when   = 0 , G = H
 T P
- since G  H = TS by comparison
 E 
 TS  nFT  
 T P
and (solving for change in entropy)
 E  dE r S
S  nF    
 T P dT nF
- combining equations - standard reaction enthalpy:
 dE 
r H  r G  Tr S  nF E  T 
 dT 
 applications
(1) Electrochemical series
= arrangement of redox couples in the order of their
reducing power
= from cell potential (reduction potentials)
E(Zn2+/Zn) = 0.76 V < E(Cu2+/Cu) = +0.34 V

* Zn has a thermodynamic tendency to reduce Cu2+

Zn(s) + CuSO4(aq) = ZnSO4(aq) + Cu(s)
* K = 1.5 x 1037 at 298oK, K >1
 applications
(2) Solubility Constants
S = solubility = molality of the saturated solution
* consider the reaction: MX(s) = M+(aq) + X(aq)
K = aM+aX  Ksp or KS= solubility product
= at very low solubility :
  1, a = m/mo , and S = m
KS = (S/mo)2 and S  (KS)1/2mo
applications
(3) Measurement of pH and pK

= hydrogen electrode : 2H+(aq) + 2e  H2(g)

fH2
Q n=2
aH  2

= potential of a hydrogen electrode

RT since E = 0
E  E  lnQ
o

nF
RT fH2
then, E   ln 2
nF a 
H
 applications
or RT fH2 RT aH
2

E H H2    ln 2  ln
nF a  nF fH2
H
since n = 2
2
RT aH
E H H2   ln
F f H2 
1/2

= the equation shows:

- increasing activity of H+, increases the tendency of
the (+) ions to change at the electrode

- predicts the E increases as the activity of H+ is

increased
 applications
at standard conditions : when f = 1

RT
E H H2   ln aH
F
but
lnaH  2.303logaH  2.303pH

therefore,
RT 2.303RT
E H H2    2.303pH   pH
F F
applications
 at 25oC
E H H2    59.16mV pH

 E is directly proportional to pH of the solution

 for each unit change in pH

 electrode potential changes by 59 mV

 each unit decrease in pH

 e increases by about 59 mV
 applications
Determination of pH
* principle: based on the measurement of the
potential of a hydrogen electrode
immersed in the solution
* assembly:
- left-hand electrode : reference electrode
- right-hand electrode : hydrogen electrode
- potential of the cell
EcellE H H2   Ereference   59.16mV pH  Eref
or E cell  Eref
pH 
 59.16mV
 applications
 in practice - glass electrode
= glass electrode
- sensitive to hydrogen ion activity
- has potential proportional to the pH
- more convenient to handle than gas electrode
- can be calibrated using solution of known pH
= response of glass electrode to the hydronium ion
activity
- glass membrane : permeable to Na+ and Li+
ions but not to H+
 from pH measurements  pK determination
 applications
(4) Potentiometric Titration
- the stoichiometric point of a redox titration
- sharper change in cell potential at the
stoichiometric point
example:
Fe2+(aq) + Ce4+(aq)  Fe3+(aq) + Ce3+(aq)
half-reactions :
Fe (aq) + e  Fe (aq) E Fe3 Fe2 = + 0.77V
 o
3+ 2+
 

Ce4+(aq) + e  Fe3+(aq) E Ce4 Ce3= + 1.61V

o

 

Keq = 1.52 x 1014

 applications
during titration :
* iron couple = give rise to an electrode potential
* cerium couple = also give rise to an electrode
potential

- therefore, at any point or stage of titration -

electrode potential may be either
o RT aFe2
E E Fe3 Fe2   ln
  nF aFe3
or
o RT aCe3
E E Ce4 Ce3   ln
  nF aCe4
thank you!

jose s. solis, ph.d.

imee su martinez, ph.d.
institute of chemistry
university of the philippines
diliman, quezon city