2625 Fall 2013

2.
625 - Electrochemical Systems
Fall 2013
Lecture 2 - Thermodynamics Overview

Dr.Yang Shao-Horn
Reading: Chapter 1 & 2 of Newman, Chapter 1 & 2 of Bard & Faulkner, Chapters 9 & 10 of Physical
Chemistry
I. Lecture Topics:
A. Review 1st and 2nd laws of thermodynamics
First law: dU = Q W
Second law: IS 0
B. Chemical Equilibrium
Gr =
Gr +
nRT ln Ka = 0; where Ka =
prod
react
i = i + RT ln ai ;
II
ai i
I
ai i
i i n = 0
C. Electrochemical Equilibrium
r = G + nRT ln Ka + nzr F Er = 0
G
r
Nernst Equation: Er = Er +
RT
ln Ka
zr F
II. Review 1st and 2nd laws of thermodynamics

A. 1st Law of Thermodynamics
For a closed system of constant mass,
i. internal energy is constant: IU = 0

ii. external energy changes through work and heat: EU = Q W , where Q is heat trans
ferred into the system, and W is work done by the system. Note: in most (uid) systems,
W is PdV; for electrochemical systems, we will expand this denition to include electro
chemical work.
iii. the total energy change of the system is the sum the internal and external energy changes:
dU = IU + EU = Q W
IU and EU are intensive properties whereas Q and W are extensive properties
A. Intensive property: A physical property which does not depend on the size (volume,
mass, number, etc.) of the system
B. Extensive property: A physical property which does depend on the size (volume, mass,
number, etc.) of the system
Lecture 2
Thermodynamics Overview
2.625, Fall 13
System
IU
Environment
EU
Figure 1: The canonical thermodynamic system, with internal energy change IU and external energy change
EU .
B. 2nd Law of Thermodynamics
i. change in internal entropy is equal to generated entropy, which is never less than zero:
IS = gS 0
ii. external entropy change is the change in heat scaled by the temperature of the system:
ES = Q
T
iii. the total entropy change is, similarly, the sum of the internal and external entropy changes:
dS = IS + ES = IS + Q
T
Multiplying through by T, we have: T dS = T IS + Q
And since IS is always greater than or equal to zero, T dS Q.
These expressions can be mapped into state space. The change in entropy while U and V are
held constant, or H and P are held constant, are shown below.
C. Combining the 1st and 2nd Laws, Q = dU + P dV (where W is given as P dV )
Subbing in T dS IS for Q and rearranging, we have
T IS = dU + P dV T dS 0
(1)
For reversible processes, IS = 0, so T dS = dU + P dV . This is Gibbs fundamental equation.

Further, a closed system approaches equilibrium by maximizing entropy, S.
Lecture 2
2.625, Fall 13
At constant U, V
equilibrium
States
Figure 2: Equilibrium is achieved when entropy is maximized for a system where U and V are constant.
D. Alternatively, we can dene equilibrium by using Gibbs free energy.
i. First, we dene enthalpy, H: H = U + P V
ii. Then dene Gibbs free energy, G: G = H T S
iii. G = U + P V T S, and dG = dU + d(P V ) d(T S)
By considering the combined rst and second law equation, we can now write:
IS = dG V dP + SdT 0.
Thus, a system approaches equilibrium by minimizing G such that

dG 0 :
Lecture 2
2.625, Fall 13
At constant P, T
equilibrium
States
Figure 3: With the proper choice of variables held constant, the Helmholtz and Gibbs functions show similar
proles. Equilibrium is achieved when Helmholtz or Gibbs functions are minimized.
Note: for a reversible system, dG = V dP SdT
III. Gibbs free energy of multicomponent systems
The general form of the Gibbs free energy for a multicomponent system or phase is G(T, P, n1 , n2 , ....ni ),
where ni is the number of moles of species i in the system or phase.
dG(P, T, ni ) =
G
T
dT +
P,n
G
dP +
P T,n
G
ni
dni
(2)
T,P,nj
We can dene the partial dierentials in the above equation as follows:

G
T P,n
S =
V =
i =
G
P T,n
G
ni
r
T,P,nj 6
=ni
Then we can write the dierential from of the Gibbs free energy for a multicomponent system as:
dG(P, T, ni ) = SdT + V dP +
i dni
(3)
A. Comparing this to the expression for dG above,P

we see that the internal entropy is expressed here
as the sum of the chemical potentials: T IS = i i dni
This entropy is g
generated
when a new component i is introduced into the system, with a chemical
r
G
potential, i = ni
6 ni
T,P,nj
=
P
Looking back, recall that at constant T and P, T I S = dG = i i dni 0
4
Lecture 2
2.625, Fall 13
B. Thermodynamic quantities are typically tabulated on a molar basis, meaning that the quantity is
provided in units per mole of reactant/product. Examples are:
g : molar Gibbs free energy
s : molar entropy
h : molar enthalpy
C. We dene mole fraction: Xi = inni i
P
P
P
G=
ni gi ; where gi =
Xi gi ; and n =
ni
D. We dene the partial molar Gibbs free energy with respect to composition as:
g
r
g
r
g
G
gi = X
=
= i
ni
i
T,P,Xj 6=
=Xi
T,P,nj 6=
=ni
E. For an ideal gas, we dene the partial pressure as:

Pi = Xi P
F. We can dene a more convenient form of the chemical potential, where we write the chemical
potential of a species i in terms of its chemical potential in the reference state, i
and its activity,
ai : i = i + RT ln ai
Dening the chemical potential of a species in terms of its activity is slightly more convenient
because the activity can be described by simple models, which will be discussed next.
G. Activity models
Ideal (Raoultian) Solution: ai = Xi
An ideal solution assumes that the activity of species i is equal to the mole fraction of species
i.
Ideal Gas: ai = Pi
For an ideal gas, the activity of species i is equal to the partial pressure of species i. This is
an extension of the ideal solution model.
i. Figure ?? demonstrates how activities can be calculated from the partial pressures of gases
in a mixture.
ii. The enthalpy
of mixing can be found by calculating the enthalpy before and after mixing:
P
hinit = Pi Xi hi (T, Pi )
i (T, Pi ) = P Xi hi
hnal = i Xi h
i
hmix = hnal hinit = 0
iii. The entropy
of mixing
a similar way:
P
P can be found in
sinit = i Xi si = i Xi si R ln PPi

P
P
snal = i Xi si = i Xi P
si R ln PPi
smix = snal sinit = i Xi R ln Xi
Note that since Smix is greater than zero, mixing is irreversible. This should line up with
your intuitive understanding of gas behavior.
iv. Next, the

P Gibbs free
P energy of a mixture:
ginit = i Xi gi = i Xi gi + RT ln PPi

P
P
Pi
gnal = i Xi gi = i XP
i gi + RT ln P
gmix = gnal ginit = i Xi RT ln Xi 0
When gmix 0, mixing will occur spontaneously and work will be generated.
Lecture 2
2.625, Fall 13
Before Mixing: P1 = P2 = P3 = Pi = P
P1
P2
P
System 3
P4
n1
n2
n4
n3
After Mixing: P = p1 + p2 + p3 + pi
p1, p2, p3, ... pi
n1, n2, n3, ... ni
Figure 4: Initially, a box contains several species of a gas, each having the same pressure Pi , the same as the
overall box pressure P. After the partitions are removed, the gases mix and P is the sum of each gas partial
pressure Pi .
IV. Chemical Equilibrium
A. Condition for chemical equilibrium
X
X
i dni = 0 , or
Gr = 0 at constant T and P.
P
i i n, and i is the stoichiometric coecient of species i.
Where Gr =
Lecture 2
idni
2.625, Fall 13
At constant T, P
equilibrium
States
Figure 5: Equilibrium is achieved at constant T and P when the sum of chemical potentials of components
in the system is minimized.
B. Example
i. Consider the formation of water: H2(g) + 12 O2(g) H2 O
ii. H2(g) = 1, O2(g) = 0.5, and H2 O = 1
C. Deriving the condition for chemical equilibrium:
P
P
i. Gr =
i i n = n i (i + RT ln ai )
P
P
ii. Gr = n i i + nRT
i ln ai
P
iii. Let Gr = n i i
iv. Gr =
Gr
prod
+ nRT ln
react
prod
ai i
v. Remember that Ka =
II
ai i
II
ai i
ai i
Gr +
react
vi. At equilibrium: Gr =
nRT ln Ka = 0
vii. Thus, at we can dene the chemical equilibrium condition: Gr = nRT ln Ka

D. Two interesting relations
i. The natural
of the
constant, Ka , can be written as follows:
h logarithm
r
h equilibrium
r
G
H
Ka = exp nRTr = A exp nRTr
ln Ka = lnA
Hr
nRT
Lecture 2
ln Ka
2.625, Fall 13
H2 + 0.5O2 H2O
CO2 CO + 0.5O2
(high T)
1/T
Figure 6: Example plot of ln Ka vs.
1
T
(low T)
. ln Ka varies approximately linearly with
1
T
ii. Assuming that Hr is not a function of temperature (this is a good assumption for a wide
range of T), the following relationship can be developed:
Since Gr (T, P ) = Hr T Sr ,
Gr
= Sr , assuming that Hr = f (T )
T
Example: H2(g) + 12 O2(g) H2 O
T (K)
300
500
1000
hr (kJ/mol)
-286
-242.4
-245
gr (kJ/mol)
-237
-219
-192
Er
1.23
1.13
0.99
Lecture 2
2.625, Fall 13
Gr
T
-Sr
Figure 7: Visual representation of how the change in Gibbs free energy with temperature is approximately
equal to the change in entropy (i.e. the slope of Gr as a function of temperature is equal to Sr ).
E. Electrochemical Equilibrium
i. Relative to a chemical system, equilibrium for an electrochemical system has an additional
work term.
ii. W = Edq for charged particles with a charge of dq
X
iii. Condition for electrochemical equilibrium (at constant T and P):
i i + zr F Er = 0
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Fall 2013
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2.625 - Electrochemical Systems
Fall 2013
Lecture 3 - Chemical Potential and Equilibrium

Dr.Yang Shao-Horn
I. Review
A. 1st and 2nd laws of thermodynamics
P
B. Chemical Equilibrium: Gr = i i n = 0, at constant T and P
II. Lecture Topics
A. Electrochemical Equilibrium
r = P i i n+nzr F Er = 0,
Electrochemical Gibbs free energy (including charged species): G
at constant T and P
B. Nernst equation that governs the cell/reaction potential
Er = Er +
RT
zF
ln
prod
00
ai i
react
Er = f (T, P, Xi )
ai i
Example reactions and concentration cells

C. Electrochemical series to determine the cell/reaction potential
III. Electrochemical Equilibrium
A. The work term for charged particles under an applied potential is: W = Edq, where particles
have charge dq
P
B. dG(P,
T, n, E) = SdT + V dP + i dni + Edq, at constant T and P
X
=
C. At electrochemical equilibrium (under constant T and P): dG
i dni + Edq = 0
D. Alternatively, we can write that for electrochemical equilibirum (Gibbs-Faraday Equilibrium EquaX
tion):
i dni = Edq
Where F is Faradays constant: F = NA qe = 6.022 1023 1.6 1019 = 96500C/mol
zr is the number of charges/electrons transferred in the reaction (per mole of reactant or
product).
Example: H2(g) + 12 O2(g) H2 O;
zr = 2 per mole of H2(g)
zr = 4 per mole of O2(g)
IV. Nernst Equation that governs reaction potential
P
A.
i i = zr F Er , at (T, P )
P
B.
i i = zr F Er , at (T , P )
P
P
C.
i i i i + zr (Er Er )F = 0
D. Er =
Er
RT
zr F
ln
prod
react
00
ai i
ai i
Lecture 3
Chemical Potential and Equilibrium

0
Q
i
RT
react ai
E. Nernst Equation: Er = Er +
ln Q
00
i
zr F
prod ai
2.625, Fall 13
V. Nernst Equation for ideal reacting gases

A. Activity of gaseous species, i: ai =
Pi
P
Xi P
P
ai i
B. Er = Er zRT
ln Q react
rF
00
i
prod ai
C. Er =
Er zRT
rF
ln Q
react
prod
D. Er =
Er
RT
+
ln
zr F
Where
i =
( PPi )
( PPi )
P
P
0
i
00
i
P i
0
Q
i
RT
react Xi
+
ln Q
00
zr F
X i
prod
00
E. The reaction potential, Er is ultimately a function of a temperature dependent term, system

pressure dependent term, and a concentration dependent term.
i. Temperature dependent term: Er = Er =
Er
T
s
r
zr F
gr
zr F
= f (T, P )
=
The temperature dependent term can be significant. For example consider the reaction:
H2(g) + 12 O2(g) H2 O.
At 300K, Er = 1.23V
At 1000K, Er = 0.99V
P2
ii. Pressure dependent term: Er = zRT
ln P
rF
1
Varying the pressure only can only provide a small gain when increasing from very low to very
high pressures in terms of thermodynamics (pressure variations can, however, have a large
impact on kinetics). For example consider T = 300K, zr = 4, P1 = 1atm, and P2 = 10atm.
Then: Er = .056V.
ln PPab
iii. Concentration dependent term: Er = zRT
rF
The concentration dependence also does not greatly affect the reaction potential, but again,
it can have important kinetic effects.
For example, consider T = 300K, zr = 4, P1 = .21atm, and P2 = 1atm.
Then: Er = .01V.
F. Nernst Equation for ideal liquids/solids: Er =
Er
0
Q
i
RT
RT
react Xi
+
+
ln Q
00
zr F
zr F
X i
prod
VI. Chemical Equilibrium vs. Electrochemical Equilibrium

A. Chemical Equilibrium
Under chemical equilibrium, no work can be generated: Gr = 0 = Gr (P = 1atm) +
nRT ln Ka
Example: Gr = zr F Er
Er = 0 and Ka is very large, so mostly H2 O is present on right side
B. Electrochemical Equilibrium
r = P
G
i i n = 0, where
i = i + zi F E.
i is the electrochemical potential.
2
Lecture 3

r = P i i n + nzr F Er = 0
Thus, we can write: G
Example: H2(g) + 12 O2(g) H2 O(l)
a a
Gr = Gr + nRT ln aHH2 OO2 , where aH2 = aO2 = aH2 O = 1
2
Gr = Gr = nzr F Er
Therefore: Er = 1.229V
2.625, Fall 13
VII. Concentration Cells

A. Concentration cells are used for desalination, hydrogen sensors, oxygen sensors, etc.
P
100atm
B. Example: gH
= gH
+ RT ln H2
2
2
PH2 (108 atm)
108 atm
gH
=
g
+
RT
ln
H
P
2
2
8
10
gr = gH
2
atm
100atm
gH
= RT ln
2
(100atm)
P
PH2 (108 atm)

PH2 (100atm)
C. Physcial Origin of the electrical potential and work generated: entropy change of mixing
D. Alternatively, desalination and gas separation requires work input due to the entropy change of
mixing
VIII. Electrochemical Series
A. The purpose of the electrochemical series is to determine the potential of individual electrodes
(half-cell reactions) with respect to a standard electrode, such as the Stanard Hydrogen Electrode
(S.H.E.).
B. Standard Hydrogen Electrode:
aH+ = aH2 = 1, T = 298K, and P = 1atm.
+
We define EH
+ 2e H2 .
+ /H = 0V for 2H
2
C. Example 1
Consider the reaction O2 + 4H+ + 4e 2H2 O, where EO

= 1.229V
+
2 ,H /H2 O
Combine:
2H2 4H+ + 4e
+
O2 + 4H+ + 4e 2H2 O
(1)
O2 + 2H2 2H2 O
EH
+ /H = Eano de = 0V
2
EO2 ,H+ /H2 O = Ecatho

de = 1.229V
Ecell
= Ecatho
de Eano de = 1.229V
D. Example 2: Consider the thermodynamic stability of the following (T = 298K and P = 1atm)
i.
ii.
iii.
iv.
Fe/H2 O
Fe/H2 O + H+
Fe/O2 /H2 O
Fe/O2 /H2 O/H+
Lecture 3

First check the electrochemical series and find relevant redox reactions:
Fe2+ + 2e Fe = EFe2+ /Fe = 0.409V
O2 + 4H+ + 4e 2H2 O = EO
= 1.229V
+
2 ,H /H2 O
O2 + 2H2 O + 4e 4OH = EO
+
= 0.401V
2 ,H /OH
2H+ + 2e H2 = EH
+ /H = 0V
2
i. anodic: Fe Fe2+ + 2e
no cathodic reaction can be found
ii. anodic: Fe Fe2+ + 2e
cathodic: 2H+ + 2e H2
Eano
dic = 0.409V; Ecatho dic = 0V
Ecell = Ecathodic Eanodic = 0.409V > 0
This reaction will occur spontaneously. Iron is not stable.
2.625, Fall 13
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Fall 2013
Lecture 4 - Electrochemical Cells

Dr.Yang Shao-Horn
Nernst Equation: = or +
RT
ZrF
ln
i
reactants ai
Q
i
prod ai
r = f (T, P, xi )
Electrochemical series of half cell reactions (P o , T o , oO/R )

Electrochemical series of half cell potentials can help us...
1. Estimate the Nernst Voltage of aqueous electrochemical reactions under standard conditions
(T o = 298K, P o = 1atm, ai = 1)
2. Understand the stability of metals in aqueous environment
Example: Metal plating vs H2 production
In an acid solution (aH + = 1), can we plate Cu spontaneously? Can we plate Zn spontaneously?
Figure 1: Electrochemical series of copper, hydrogen, and zinc

Cu Case
Cathode Cu2+ + 2e Cu, ocathode = 0.340V
Anode H2 2H + + 2e, oanode = 0V
ocell = ocathode oanode = 0.340V > 0 Will Plate
Zn Case
Cathode Zn2+ + 2e Zn, ocathode = 0.763V
Anode H2 2H + + 2e, oanode = 0V
ocell = ocathode oanode = 0.763V > 0 Will NOT Plate
All metals with half cell potentials more positive than SHE can be plated out spontaneously in
aqueous electrolytes
A quick question: changing from acidic to basic solution, What/How would the driving force
change?
H + /H2 = f (pH) means that H2 2H + + 2e is pH dependent
1
Lecture 4
Electrochemical Cells
2.625, Fall 13
Cu2+ + 2e Cu is pH independent
I. Nernstian Half Cell Potential
Given a redox couple o O + Ze R R (Reduction)
o and R are stoichiometric coefficients and Z is the # of electrons
Couple O/R redox with SHE to make a chemical reaction
O O + Ze R R
+
= O O + H2 H2 R R + H + H +
H2 H2 Ze + H + H +
H
Nernst Voltage of this reaction is :cell = oR +
RT
ZF
ln
o
a
o aH
+
a H+
H
2
2
R
aR
Also, the reaction voltage can be defined as: cell = cathode anode = O/R O = R
o
thus O/R = O/R
+
RT
ZF
ao
ln aoR is the Nernst half cell potential for O/R

R
Example- Consider H2 concentration cell

Overall reaction H2 (1000atm) H2 (108 atm)
Figure 2: Hydrogen concentration cell, a high H2 pressure and low H2 pressure chambers are
separated, only allowing for H + ion transport
o
anode = H
+ /H +
2
RT
2F
a2
H+
ln aanode
=0+
H2
RT
2F
a2
H+
ln P anode
=
H2
assuming ideal gas for H2 and P =1atm aH2 =

o
cathode = H
+ /H +
2
RT
2F
a2
H+
ln acathode
=0+
H2
cell = cathode anode =
RT
2F
RT
2F
RT
2F
a2
H2
P anode
H2
ln P cathode
= 0.295V
H2
II. Pourbaix Diagrams

Potential-pH diagrams established by Pourbaix in 1974
Example: Stability of water in aqueous electrolytes
aH + = H +
[H + ]
[H + ]o
activity of solution species

2
H2
P H2
Po
H+
ln P cathode
=
a. Consider hydrogen electrode potential vs. pH

2H + + 2e H2
1
ln P anode
RT
2F
1
ln P cathode
H2
Lecture 4
2.625, Fall 13
activity coefficient = 1 for ideal solution

[H + ] molar concentration of H + mol/L
[H + ] molar concentration of H + at 1 mol/L (1M)
P o = 1atm, T o = 298K, oH + /H2 = 0, aH + = 1
Recall that ln x = 2.303 log x and pH = log[H + ]

H + /H2 = 2.303RT
log PH2 + 2.303RT
log[H + ]
2F
2F
log PH2
H + /H2 = 2.303RT
2F
2.303RT
2F
pH Hydrogen Electrode
At room temperature, 298 K, Hydrogen electrode potential as f (pH, PH2 ):

H + /H2 = 0.059 2 log PH2 0.059pH
As pH , H + /H2 ; PH2 , H + /H2
b. Consider the oxygen electrode
1
+
2 O2 + 2H + 2e H2 O(l) 298K
1/2
O2 ,H + /H2 = oO2 ,H + /H2 +
RT
2F
ln
2
aO a H
2
2
aH2 O(l)
=1
1/2
T
O2 ,H + /H2 = oO2 ,H + /H2 + 2.303R
log PO2 a2H + (ideal gas)
2F
Oxygen electrode potential at room temperature
O2 ,H + /H2 = 1.229 + 0.0148 log PO2 0.059pH

As pH , O2 ,H + /H2 ; PO2 , O2 ,H + /H2
c. Pourbaix diagram of water
Figure 3: Pourbaix diagram of water, showing regions of gas evolution and water stability
Physical significance of Pourbaix Diagram
i. H + /H2 half cell reaction (from pH = 0(aH + = 1) to pH = 14)voltage decreases by
0.82V (0.059V 14). 2H + + 2e H2 reduction less thermodynamically favorable.
ii. O2 , H + /H2 O half cell reaction voltage decreases by 0.82V from pH = 0 to 14. 2H + +
O2 H2 O reduction less thermodynamically favorable.
III. Description of electrochemical cells
For any electrochemical cells, we need at least:
A. Two electrodes (one for oxidation, one for reduction) to provide electrons
3
Lecture 4
2.625, Fall 13
B. One ion conduction to provide ionic transport from one electrode to another. Must no
conduct electrons
C. External electrical circuit to provide electron flow from one electrode to another
Generally speaking, we have two type of cells
A. Galvanic Cells: cell > 0 and GR < 0. Reactions can occur spontaneously to produce
work. Examples include primary batteries, fuel cells, secondary batteries upon discharge,
flow batteries, and capacitors upon discharge.
B. Electrolytic Cells: cell < 0 and GR > 0. Electric work is needed to drive the reaction.
Example is water electrolysis to produce H2 .
i. Production of Al, Li, Na, K, Mg, and Zn by electrolysis
ii. Production of Chlorine and NaOH for water purification
+
+ 2e H2,(g) , oH + /H2 = 0V
Cathode 2Haq
Anode 2Claq
H2,(g) + 2e, oCl /Cl2 = 1.358V
2N aCl + H2 O Cl2 + H2 + 2N aOH
Historical Note: Invented as a weapon in WWI by Fritz Haber (Nobel Laureate in
Chemistry). Haber-Bosch N2 + 3H2 2N H3 .
Figure 4: Schematic of cell types. Galvanic cells produce work during the reaction. Electrolytic
cells require work or energy to drive the reaction.
IV. Faraday law i m,
i in C/s, m
in g/s
Michael Faraday (1791-1867). Discovered water electrolysis and coined the terms anode, cathode, ion and electron.
i=
m
M
ZrF
t
in C/S or A
m weight of reactant or product (g)

M molecular weight of reactant or product (g/mol)
F Faraday Constant = 96485 C/mol 96500 C/mol
Zr # of electrons involved
4
Lecture 4
2.625, Fall 13
Example: To make H2 at 1g/s, what current is needed?

i=
m ZrF
t M
1g
s
96500C/mol
2g/mol
105 C/s = 105 A
Large current needed (1g/s 105 A) due to large F

Consider H2 /O2 electrolytic cells to make H2 using electricity at 1 A/cm2 and cell area of
105 cm2 , providing current at 1A and cell voltage is 1.6 V.
To make 1 kg H2 105 A 1000s = 108 C
From t =
mZrF
iM
Energy needed
=
8
1kg 296500C/mol
105 C/s2g/mol
10 C 1.6V
3600J /W h
= 1000s
44kW h
Assuming $0.15/kWh, electricity cost of $7/kg for H2 .

Current H2 , $10/kg and target cost of $3/kg.
V. Electrochemical energy conversion efficiencies
Maximum thermal efficiency- Thermodynamics
W
G
S
ideal = H
= H
= 1 TH
Second Law efficiency (voltage efficiency)
= Emeasured
Eo
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Fall 2013
Fall 2013
Lecture 8 - Kinetics of Chemical and Electrochemical Reactions

Dr.Yang Shao-Horn
I. Overview
A. For a given O + e
R:
i. Electrode kinetics lead to activation losses. a is defined as the overpotential loss due
to kinetic limitations and is called the activation polarization (a ln i). Electrode kinetics
include:
Electron transfer
Ion/molecule adsorption
Ion/molecule desorption
ii. Ion/mass transport gives rise to ohmic losses ( ) and concentration losses (c ). ( i)
and (c exp(i))
iii. Overpotential loss curves for electrolytic cells and galvanic cells a are shown below.
Electrolytic cell: Ecell = Eeq + a + c +
Galvanic cell: Ecell = Eeq a c
iv. Further, schematic plots showing common losses in electrochemical capacitors, lithium batteries, fuel cells, and electrolytic cells are also shown below.
Electrode
Electrolyte
Osurface
e-
Obulk
Oads
Bulk
Solution
Rads
Rsurface
Rbulk
Figure 1: Schematic of transport and kinetic steps which must occur during a single electron transfer reaction.
Lecture 8
Kinetics of Chemical and Electrochemical Reactions

E
Electrolytic Cells:
2.625, Fall 13
Galvanic Cells:
Eeq
a
Eeq
Figure 2: Overpotential losses as a function of

current common to an electrolytic cell.
Figure 3: Overpotential losses as a function of

current common to a galvanic cell.
Electrochemical Capacitor
(typically limited)
Li-Battery Cycling
(typically transport (c) limited)
Eeq
Charge
Charge time
Figure 4: Illustration of ohmic overpotential

losses in an electrochemical capacitor.
Figure 5: Lithium battery potential as a function

of time during battery cycling.
Lecture 8
2.625, Fall 13
Fuel Cells or
Electrolytic Cells
Kinetics (a) limited
Figure 6: Current as a function of potential for a kinetically limited device.

II. Key Concepts Covered
A. Chemical kinetics: basic concepts
i. Arrhenius expression
ii. Transition state theory
iii. Why catalysts?
B. Surface thermodynamics: basic concepts
i.
ii.
iii.
iv.
Physisorption
Chemisorption
d-band center theory
Langmuir isotherms
C. Electron transfer kinetics

i. Adding e transfer to transition state theory
ii. Butler-Volmer Equation
III. Basic Concepts in Chemical Kinetics
A. The rate of chemical reactions
kf
[A] [B]
kb
for a homogeneous reaction (single phase) is given by:
d[B]
Homo
3
i. Rchem
= d[A]
dt = dt = kf [A] kb [B] mol/cm
This equation is valid for a single reaction in a closed system with constant volume.
[A], [B]: molar concentration of A or B in mol/cm3
kf , kb : forward/backward reaction rates in 1/s (kf and kb are functions of temperature,
but not [A] or [B])
Homo
ii. When kf >> kb , then Rchem
= kf [A]
d[A]
dt = kf [A]
d[A]
dt = [A]t=0 exp (kf t)
having
and
Lecture 8
2.625, Fall 13
Transition State Theory
G# > 0
H2 + 0.5O2
Gr < 0
(driving force)
H 2O
Reaction Coordinates
Figure 7: Gibbs free energy as a function of reaction coordinate for the formation of water from oxygen and
hydrogen. The free energy curve exhibits a reaction barrier which limits how fast the chemical reaction can
occur.
~
G
Butler-Volmer Equation
(electrochemical rxn)
~
G#
O + e-
Figure 8: Reaction barrier for a single electron transfer electrochemical reaction. This reaction governs the
Butler-Volmer equation, which will be discussed in a later lecture.
Lecture 8
2.625, Fall 13
[A]
[A] @ t=0
Time
Figure 9: Concentration of reactant A as a function of time as the chemical reaction proceeds.
Homo
iii. When the reaction reaches equilibrium, Rchem
=0
A. kf [A]eq = kb [B]eq
B.
kf
kb
[A]eq
[B]eq
Ka , where Ka is the equilibrium constant
prod
C. Ka =
00
Xi i
react
Xi i
h
D. Ka =
[XB ]eq
[XA ]eq
nB
n +n
h A B
nA
nA +nB
i
ieq
eq
[ nVB ]eq
=
[ nVA ]eq
[B]eq
[A]eq
B. Law of mass action

0 0
k
0
f
i. Reactants 1 , 2 , ...i P, for (kf >> kb )
0
Q
i
ii. R = dP
react [i]
dt = kf
kf
e.g. aA + bB + cC P
c
a
b
iii. R = dP
dt = kf [A] [B] [C] , where a, b, and c are reaction orders
C. Arrhenius expression of chemical reactions
i. Remember:
kf
[A] [B]
kb
ii. and: R = d[B]

dt = kb [B] + kf [A], where kf , and kb are functions of temperature but are
independent of the concentrations of A and B.
iii. In 1889, Arrhenius introduced the concept of an activation barrier:
A. Recall from chemical equilibrium: Gr = 0 = Gr + RT ln Ka
Sr
Hr
R RT
H
= RT 2r
ln Ka =
d ln Ka
dT
Lecture 8
2.625, Fall 13
kf or kb
T
Figure 10: Temperature dependence of kf and kb .
B. Arrhenius proposed a similar expression for reaction rate constants
Eaf
RT 2
Eb
= RTa2
where Eaf > 0
d ln kf
dT
d ln kb
dT
and Eab > 0. These are called activation barriers for the forward/backward
reactions.
C. The activation barriers are related to the change in enthalpy of the reaction by:
Hr = Ebf Eab

Ef
kf = Af exp RTa

Ef
kb = Ab exp RTb
D. Typically, Af , Ab , Eaf , and Ebf can be obtained from fitting experimental data:
Lecture 8
ln Ka
Exothermic
o
Hr <0
Endothermic
o
Hr >0
(high T)
1/T
(low T)
Figure 11: Behavior of ln Ka for both exothermic and endothermic reactions.
Ea
A
o
Hr
Ea
Figure 12:
2.625, Fall 13
Lecture 8
2.625, Fall 13
ln kf
-Eaf
R
(high T)
1/T
(low T)
Figure 13: Activation energy barrier as proposed by Arrhenius.

IV. Transition State Theory - 1935 (activated complex theory)
kf
A. We began with the model that a species transforms from reactant, A to product, B: A B.
#
B. Now consider the formation of an intermediate species called the Activated Complex (AB) :
#
# kf
K#
A a (AB)
where
Ka# is

Ka# = exp
the equilibrium constant between A and (AB)

#
G
RT
and, kf# is the reaction rate constant from (AB)

h
i
#
#
C. R = d[B]
=
k
(AB)
= kf# Ka# [A] = kf [A]
f
dt
D. kf =
kf#

exp
G#
RT
to B
i. The jumping frequency of a species is given by: kBhT 1013 1/s.

where kB is the boltzmann constant, T is temperature, and h is Plancks constant.

H #
#
kB T
G#
G#
ii. kf = kf exp
= h exp RT
= Af exp
RT
RT
where G# = H # T S #
V. The influence of catalysts on the rate of chemical reactions
A. criteria for a catalyst in chemical reactions
i. increase reaction rates
ii. not consumed in the reaction
iii. a small quantity increases the reaction rate of a large amount of reactants
Lecture 8
2.625, Fall 13
E
(AB)#
G#
#
Figure 14: Free energy barrier for a reaction to proceed from A to B, where a transition state species, (AB) ,
is formed as an intermediate.
without catalyst
E
(AB)#
(AB)#
c
Gf,c
#
Gf#
with catalyst
Figure 15: When a catalyst is introduced, the free energy barrier for formation of the transition state
decreases.
Lecture 8
2.625, Fall 13
Rchem
ln Kads
Figure 16: Typical volcano curve showing how the rate of the chemical reaction changes a function of
equilibrium constant for adsorption.
iv. does not shift chemical thermodynamics of Ka
B. Transition State Theory with a catalyst
K#
# kf
i. A a (AB) B
#
Ka,c
# kf,c
ii. A (AB)c B
iii. The rate change between the reaction without a catalyst and the reaction with a catalyst is
given by:
!
kf,c [A]
kf [A]
kf,c (AB)#
c
kf (AB)#
[
[
]
=
]
exp
#
f,c
RT
exp
#
f
RT
where G#
f,c is dependent on the catalyst.
C. Sabatier Principle (Heterogeneous Catalysis)
i. Homogeneous reactions reactions occur in one phase: R = kf [A] kb [B] mol/cm3 s
ii. Heterogeneous reactions reactions occur in multiple phases
iii. Rchem = kf [A]ads kb [B]ads , where [A]ads is given in mol/cm2
kf
A B, or
kf ,c
A B
10
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Fall 2013
Lecture 9 - Surface Reactivity and Electronic Structure

Dr.Yang Shao-Horn
Topics to be covered in the lecture
I. Sabatier principle for heterogenous reaction
II. Basic concepts of thermodynamics= Physisorption/Chemisorption
III. Langmuir Isotherm
Homogenous reactions: Reactions occur in one phase
Heterogenous reactions: reactions occur is multiple phases
Examples
N2 + 3H2 2N H3 (Haber Process)
H2 + 12 O2 H2 O
CO + 12 O2 CO2
I. Sabatier Principle for heterogenous reaction kinetics
The best catalysts are surfaces that bind reactant/product neither too weakly nor too strongly
Activity/rates
Just right
Too weakly
Too strongly
ln Kads
Figure 1: Schematic of volcano relationship

Recall homogenous reactions
#
G
f,c
RT

#
G
exp RTc
exp
kf c
kf
>1
Where the reaction rate constant can be increased by catalysts via lowering the reaction
barrier.
kf
A B (assuming kf >> kb for simplicity)

1
Lecture 9
Surface Reactivity and Electronic Structure

(AB)#, without catalyst
2.625, Fall 13
(AB)#, without catalyst
Gf#
Gf#
(AB)C#, with catalyst
(AB)C#, with catalyst
Gf,c#
Gadso
(a) catalyst vs no catalyst
kf#
k#
(b) absorbed catalyst vs no catalylst
ac
C + A ads
AC
(AB)#
BC B + C where C represents the catalyst
C
or we write if Bc B + C is barrier-less
kf#
k#
ac
C + A ads
AC
B + C
(AB)#
C
Rchem for heterogenous reaction has a unit of mol/cm2 s

#
#
Rchem = kf# [(ABC
] = kf# [AC ]Kac
, where [AC ] is the moles of A adsorbed on the catalyst
2
surface in mol/cm .
#
Rchem = kf# Kac
[A]Kads Lc ky

Go
Letting [AC ] = [A]Kads LC , where Kads is the adsorption equation constant exp RTads
and LC is the characteristic length of adsorption.
In mol/cm2 [AC ] = Jsurf ace , where Jsurf ace is the flux of molecules hitting the surface in
mol/cm2 s and is the residence time of an absorbed species in (s).
vgas |
Jsurf ace = 41 [A]gas |
[A]gas =
ngas
V
= o exp
P
RT
Go
ads
and |
vgas | is the average velocity of gas in 3D.

RT

Go
[AC ] = 14 [A]g as |
vgas | o exp RTads = [A]gas Lc Kads , where LC = 14 [A]g as |
vgas | o
#
Rchem = kf# Ka,c
[A]Kads LC
#
kf,c = kf# Ka,c
Kads LC cm/s for heterogenous reaction rate constant

kb T
#
Kads LC
kf,c = h Ka,c

kf,c
kf
kb T
#
Ka,c
Kads LC
h

kb T
Ka# LC
h
#
Ka,c
Kads
Ka#
catalyzed
o
Sabatier principle came from the fact that G#
f,c = b agads , where the reaction barrier scales
with adsorption energy and b and a are constants.

aGo
Go
b
ads
ads
Rchem = kbhT exp RT
exp
exp
[A]Lc
RT
RT

G#
aGo
f,c
b
#
ads
where exp RT
exp
=
K
=
exp
a,c
RT
RT
Lecture 9

b
RT

Go
+ ln [A]Lc + (1 a) RTads = constant + (1 a) ln Kads
Rchem
ln Rchem = ln kbhT
2.625, Fall 13
RDS1
a<1
RDS2
a>1
Two different RDS
ln Kads
Figure 3: Volcano Diagram Relation to RDS

See slides on volcano trends
II. Basic concepts of surface thermodynamics (adsorption)
Physiosorption
Chemisorption
Polarization
large electron exchange
Van der Waal attraction
chemical bond formation
Typically not stable at RT 2.5kJ/mol at

298K
strong 1eV (100 kJ/mol)
Physisorption
Surface
Chemisorption
Surface
molecule
molecule
pushing
pushing
Potential Energy
Potential Energy
A+C
Hads
req
A+C
Figure 4: the depth of the well is a measure of the strength of absorption Habs while req represents
the bond distance between A and C
Physiosorption +dissociative chemisorption
e.g. H2 + P t + P t HP t + HP t
Lecture 9
2.625, Fall 13
Eaads>0
Eades
Physisorption
chemisorption
Figure 5: Activated molecular adsorption
Figure 6: Activated molecular adsorption for H2 and Pt

Hads = 2UHP t UHH < 0 where U represents the bond strength of H-Pt and H-H
respectively. If this condition is met, the process is thermodynamically feasible.
Examples with be seen on next lecture
O2 on P t 370kJ/mol
H2 on P t 50-60 kJ/mol
CO on P t 140 kJ/mol
III. Langmuir Isotherm
= Kads P relates the coverage of adsorbates to gas pressure/concentration at a given

temperature.
Historical note: formulated in 1916, received 1932 Nobel Prize in Chemistry
Assumptions:
Lecture 9
2.625, Fall 13
adsorption on homogenous surface

terminated upon completion of one adsorbed monolayer
adsorbed atoms do not interact with each other
adsorption
A + 2C(1 ) Ac () monoatomic gas adsorption
Gads = Goads + RT ln
aAC
P
aac PA
o
where P o = 1
At equilibrium Gads = 0 Goads = RT ln a2CaAC

(1) + RT ln PA where aAC =

o
( )
G
exp RTads = 1
PA
= Kads PA monoatomic gas adsorption

1
2
1 = (KP )) dissociative adsorption such as H2 , O2 , N2 , ...
Consider
= KP or =
KP
1+KP
log P
Figure 7: vs P and vs log P

At a given T,
T1
T2
T3
log P
Figure 8: |Hads | , Kads . 1 at higher P
At a fixed Hads
Lecture 9
|Hads1|>|Hads2|>|Hads3|
|Hads2|
|Hads1|
|Hads3|
log P
Figure 9: T , Kads . 1 at higher P
2.625, Fall 13
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Fall 2013
Lecture 13 - Butler Volmer Equation

Dr.Yang Shao-Horn
I. Lecture topics: Butler Volmer Equation

A. Application of Transition State Theory to O + e R (one-electron, one-step reactions)
B. Current is linearly proportional to potential at low overpotentials
C. Current is exponentially related to potential at high overpotentials (i.e. i exp(E))
II. Reading Materials: Chapter 3 of Bard & Faulkner
III. Pseudocapacitance
A. Recall the lab demo in which cyclic voltammetry of platinum in aqueous solutions was performed:
B. Pt in 1M HClO4
C. RHE: reversible hydrogen electrode (H2 at 1 atm at the pH of the reaction of interest)
D. EDLC: electrical double layer capacitance
+
+
Pt
E. Pseudocapacitance: HPt
ad H + e and e + H Had
F. Redox on the surface

G. What is the source of H+ ? Decomposition of H2 O
H2 O + e HPt + OH
or H2 O O2 + 4H+ + 4e (counter)
2H+ + 2e 2HPt
IV. Transition State Theory for one-step and one-electron transfer reactions
A.
kf
O + e R
kb
i.
: electrochemical potential
ii.
= i + zi F E
iii. At electrochemical equilibrium, Rel

=0
h ectrochem
i
0
A. Rel
ectrochem = kf [O] and kb R
B. Where unlike chemical reactions, kf and kb are f (T, [X ] , P, E) such that Rchem or
kchem = f (T, P, [X ])
iv. Assuming [O]surf ace = [R]surf ace

G#
kb T
f
Then: kf = kb = k = h exp RT
Lc
Where Gf# are kinetic barriers and typically very difficult to measure or compute.
Generally Gf# = C Gads , where C is a constant and Gads applied to the rate
determining step.
Lecture 13
Butler Volmer Equation
2.625, Fall 13
i
Only EDCL Remains
Increasing
scan rate
EDCL
HadH++e-
E vs. RHE
H++e- Had
EDCL
Pt electrode
Figure 1: Schematic representation of how the psuedocapacitance of platinum varies with scan rate. At low
scan rates, hydrogen adsorption and desorption peaks are visible. At high scan rates, on the electrochemical
double layer capacitance (EDCL) can be observed.
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
Figure 2: Diagram of the EDCL.
Lecture 13
2.625, Fall 13
H2 transport limited
BulterVolmer
Bubbling Ar
E vs. RHE
H2 transport limited
Figure 3: Schematic showing i-E curve for platinum pseudocapacitance, Butler-Volmer dominated hydrogen
evolution/reduction, and H2 transport limited currents.
O + e-
o,#
Gf
Figure 4: Graphical representation of the free energy of formation of the transition state.
Lecture 13
2.625, Fall 13
O + e-
Gf
o,#
o,#
Gf +(1-)Fa
o,#
Gf +Fa
Figure 5: Role of the transfer coefficient in reaction behavior.

B. At E 6= Eeq (or finite activation overpotential: a = E Eeq ), where the potential loss is used
to promote the reaction rate, the energy of the electrons is lowered by |a | relative to Eeq as E
increases, promoting the oxidation reaction rate.
i. Energy loss is given by a F .
ii. We define . which is the transfer coefficient. A typical value of the transfer coefficient is
= 0.5.
iii. Energy loss term due to impeding the forward reaction: a F .
iv. Energy loss term due to promotion of the backward reaction: (1 ) a F .
v. Derivation of the Butler-Volmer Equation:

G#
A. kf = kbhT exp RTf Lc

G#
kb T
f F a
B. = h exp
Lc
RT

aF
C. k exp
Lc
RT

G#
D. kb = kbhT exp RTb Lc

aF
E. k exp ()
Lc
RT
F. Relectrochem = kf [O] kb [R] mol/cm2 s
G. i = Zr F RAelectrode
Where ZR is the number of electrons transfered (Zr = 1)
Aelectrode is the electrode surface area
F is Faradays constant
i is current
H. assuming [O] = [R] = [O]bulk = [R]bulk ; (assumes no transport limitations)

F a
(1 ) F a
I. Butler-Volmer Equation for Electrode Kinetics: i = io exp
exp
RT
RT
4
Lecture 13
2.625, Fall 13
increasing io
E vs. RHE
Figure 6: Change in Butler-Volmer i-E curve with changing exchange current density (io .
J. io = F Ae lectrodek [O]bulk = F Ae lectrodek [R]bulk
V. Special cases of Butler-Volmer Equation
A. When |a | 10mV, i-E curve exhibits linear behavior.
i. For small values of x:
A. exp (1 + x) 1 + x
B. exp (1 x) 1 x
o F a
ii. i = iRT
From the linear region, the current exchange current (io ) can be calculated.
B. Tafel relation
i. The Tafel relation applies at large overpotentials (i.e. |a | 120mV).

|a |
ii. iifb = exp FRT
>> 1, (where if can be neglected)

a
iii. i = io exp (1)F
RT
iv. a =
RT
(1)F
ln io +
RT
(1)F
ln (i)
v. Tafel relation: a = a + b log i

vi. Example:
A. 2H+ + e H2
B. Tafel reaction:
2Had
H2

1
ads =
(KP ) 2
1+(KP ) 2
C. Volmer Reaction: 2ad + H+ + e Had .

The Volmer reaction is the rate limiting step.

#
D. io = F Aelectrode kads
n = F Aelectrode exp G
ads
RT
n : the number of adsorption sits per electrode area.
G# = C Gads , where C is a constant.
5
kB T
h
n C/s
Lecture 13
2.625, Fall 13
ln |i|
Eeq
E vs. RHE
Figure 7: Typical Tafel plot, showing E vs. ln |i|, for the Butler-Volmer equation.
10 mV
E vs. RHE
Figure 8: The linear region of Bulter-Volmer i-E curve occurs at small overpotentials.
Lecture 13
2.625, Fall 13
log |i|
Tafel Slope
Eeq
E vs. RHE
Figure 9: At high overpotentials the logarithm of the current is linearly proportional to the overpotential,
as exhibited by the linear Tafel slope.

ads
ads = exp G
P , for low ads
RT

Gads
io exp RT
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Fall 2013
Lecture 17 - Controlled Current Methods and Potential Step Methods

Dr.Yang Shao-Horn
Motivation of Transport
O2 gas
Pt
H+
Current Collector
Figure 1
H2/O2
H2/Air
iL
i
1.5A/cm2
Figure 2: Fuel Cell. Reaction rate is transport limited [O2 ] surface limiting, e.g. electrode
flooding air vs. pure O2
Increasing
current
Capacity
+
Figure 3: Lithium ion battery. Limited by DLi
in liquid electrolyte.
dissolved [O2 ] << [O2 ]gas , KOH
liquid
gas
DO
< DO
2
2
Dissolved oxygen at a concentration of 9.5 104 M is reacted at the limited current from a 5M
KOH solution, where the diffusion coefficient of oxygen is estimated to be 2.3 105 cm2 /s. The
diffusion layer near the electrode can be treated as a stagnant region of thickness 50 m.
1
Lecture 17
Controlled Current Methods and Potential Step Methods

5
2.625, Fall 13
9.510 C/cm
jL = nPoJ[O]F
= 4965002.310
= 1.69mA/cm2 O+ 2H2 O + 4e 4OH
50106 100cms
o
much slower than 1.5A/cm2 achieved in fuel cells.
Mass Transfer
Reading: Bard and Faulkner Chapter 4, Newman Chapter 11
1. Modes of mass transfer

1. Diffusion: movement of a species under the influence of a gradient of a chemical potential
(i )
2. Migration: movement of a charged particle under the influence of an electric field E (a gradient
of electric potential ).
3. Convection: stirring or hydrodynamic transport of fluid particles
2. Nernst-Plank Equation for mass transfer toward an electrode
Ji (x) = Di [i])x
x
Zi F
RT

Di [i] x
+ [i]ux
a. Ji (x): flux of species i mol/s/cm2

b. Di [i])x
x : diffusion

iF
c. ZRT
Di [i] x
: migration
d. [i]ux : convection
Solution/Electrolyte
Ji(x)
Electrode
Figure 4: Schematic of electrolyte solution flux into electrode.

Di : the diffusivity of species i in the electrolyte cm2 /s

: electrical field V/m
x
ux : velocity of fluid/electrolyte particles in the x direction (cm/s)
1. Thermodynamic driving for for diffusion and migration
Points
J ! i
Point r
Figure 5: Diffusion + migration driven by electrochemical potential
Lecture 17
2.625, Fall 13
i (r) = oi + RT ln ai (r) + Zi F (r)

i (s) = oi + RT ln ai (s) + Zi F (s)
i [i]
Ji = DRT
i
i [i]
With convection Ji = DRT
2i + [i]u
assuming ai = [i] for ideal solutions and 1D transport
i
Ji = [i]D
RT
x [RT ln[i]] + x [Zi F ] + [i]ux
Ji = Di [i]
x
Di [i]Zi F
RT
x
+ [i]ux Nernst-Plank Eq.
2. Current density associated with the flux to the electrode

ji = zi F J)i if species i is charged with valence of zi
P
P
P
P zi2 F 2
P

j = i ji = i zi F Ji = i Zi F Di [i]
i RT Di [i] x +
i Zi Fi [i]ux total current
x
from all charged species
P
as i zi [i] = 0 due to electroneutrality
P zi2 F 2 [i]D
P
D
M
where
j = i zi F D [i]
i
x
RT
x = i + i
P
Diffusion current iD = i zi F D [i]
x
P z2 F 2 [i]D
Migration current iM = i i RT x
3. Current density in the electrolyte is j M as concentration gradients are generally small
ji = jiM =
zi2 F 2 [i]Di
RT
x
|zi |F Di
RT
We definite mobility
/=
Absolute mobility
ji =
jiM
/B
i
Di
RT

|zi | F /i [i] x
ui
d
dx
cm mol/Js

= i x

ji = i x
Ohms law
i = |zi | F /i [i]: The conductivity of species i in the solution

P
P
P

j = ji = i |zi | F /i [i] x
= i x
Transference number: ti =
ji
j
|z | [i]
P i /i
/i [i]
i |zi |
i
P
i
ti is unitless 0 ti 1
Ion Conduction/Conductivity is much lower than electron conduction in metals (106 S/cm)
Electrolyte Material
Conductivity
1
ti
KCl
Aqueous HCl
H+ in Nafion
10 to 10 S/cm at 25 C
101 to 103 S/cm at 80 C, high RH
tK+ = 0.5
tH+ = 0.8
tH+ = 1.0
Nonaqueous LiPF6 in
EC:DEC
102 to 103 S/cm at 25 C
tLi+ 0.2 0.4
102 S/cm at 800 C
tO2 = 1
Solid State YSZ
4. Mixed migration and diffusion near an active electrode

j = jD + jM
3
Lecture 17

Cu(CN)2
Cu2+
jD
e-
2.625, Fall 13
jD
e-
jM
jD
e-
jM
D
M
Figure 6: A. Cu2+ + 2e Cu, j = j D + j M B. Cu(CN )2
4 + 2e Cu + 4CN , j = j j
D
C. Cu(CN )2 + 2e Cu + 2CN, j = j
Example: O2 + H2 O + 4e 4OH
Would the concentration of the following electrolyte change near the electrode? Sketch the
concentration of:
e-
MM+
Figure 7
a. NaOH
D
M
+ jOH
= jOH (Faradaic Current)
OH = Na+ jOH
e-
O2
D
M
j Na+
j Na+
=0
M
D
M
D
,jN
,jOH
Figure 8: Electrode concentration graph for NaOH, jOH
a+ , jN a+
b. NaCl
D
M
j Na+
= j Na+
e-
D
Cl
= j
j Na+ = jCl = 0
M
Cl
O2
OH-
D
M
Figure 9: Electrode concentration graph for NaCl, jOH
iOH , (jOH
<< j M )
5. The effect of ti on the limiting current

M
iR = iD
R + iR Consider a charged species, R, on the electrode surface
2 B
iR = F ZR DR [R]A F 2 ZR
/ R [R]A = F ZR DR [R]A + tR iR
tR =
iR =
[R]
iM
R
iR
F ZR DR [R]A
1tR
iR (1tR )
= F ZR DR A
Lecture 17
if tR = 1, [R] = 0. As tR , |[R]|
iL
F ZR DR [R]bulk
(1tr )o
tR , iL
Example: Lithium ion batteries
Separator/
Electrolyte
25 m
iLi+
Carbon, 200m
LiCoO2, 200m
Figure 10: The Rate of lithium ion batteries is limited by DLi in the liquid phase of the
electrode (200m)
Concentration Overpotential
[O]
[O] Bulk
[O] Surface
Figure 11: Oxygen concentration surface to bulk

O+eR
surf,O/R = oO/R +
[O]surf
RT
F ln
[R]
[O]bulk
RT
o
bulk = O/R + F ln [R]
[O]surf
/c = surf + bulk = RT
F ln [O]bulk
/i =
RT
F
ln

iL i
L
RT
F
ln 1

i
iL
[O] Bulk
o+eR
o
Figure 12
[O]surf
[O]bulk
=1
i
iL
j = F Do [[O]bulk [O]surf ] A
5
2.625, Fall 13
Lecture 17
o
jL = F D
o [O]bulk A the limiting current

Concentration overpotential /c = RT
ln
1
F
i
iL
2
3
/
(ohmic, electronic+ionic) 2. /c (concentration overpotential) 3. /a
Figure 13: 1. i = R
(activation overpotential)
2.625, Fall 13
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Fall 2013
Lecture 2 0 - Basics of Impedance Measurements.

Dr.Yang Shao-Horn
Reading: Bard and Fauklner, Chapter 10, P. 369-387
a. Proton conductivity in Nafion membranes
b. Kinetics of microelectrodes for oxygen reaction
Potential step measurements
drive the system far from equilibrium
We study the transient response, and determine parameters like D, ti , etc.

Impedance measurements
perturb the system with an alternating current / voltage magnitude.
Advantages:
I. High precision - steady state
II. Treat the response theoretically by linearizing I {E response
III. Measurement over a range of frequencies 104 106 Hz (0.1 mHz - 1 MHz)
Electrochemical processes in an electrochemical cell
Networks of resistors and capacitors
Basics of AC circuits
E Emax sin t
is angular frequency in rad/s
2f, where f is frequency
Lecture 2
Basics of Impedance Measurements.
2.625, Fall 13
Elements
1.
E ptq
sin t
E Emax
R
R
imax sin t
i
Pure resistor
with resistance R,
ZR R
i and E are in phase
2.
Pure capacitor
with capacitance C
C E

q
charge
capacitance
i ddtE C
Emax cos t C
C Emax sinpt t q
i imax sinpt
q,
2
dq
dt
where imax
C Emax Ep max
1
q
i and E out of phase by {2.
We define ZC
j .
C
Imaginary impedance ZC
Z 2 and the magnitude of the imaginary impedance is C1
Simple circuits
1.
j
R C
Z 1 Z 2 j

real
imaginary
imped.
impedance
for a capacitor.
Lecture 2

8
0
ZR
Z2 8
The magnitude of Z:
d
|Z |
R2
1
C
The phase shift associated with the circuit:

tan
Z2
Z1
1
C
1
CR
0 for resistors and 2 for capacitors.

Impedance data are displayed typically in Nyquist plots and Bode plots below.
Nyquist Plots:
2.625, Fall 13
Lecture 2
Bode Plots:
2.625, Fall 13
Lecture 2
2.625, Fall 13
Example:
8, Z
0, Z
100
100
log |Z | log
1
R2
log
log |Z | log
R2
0
R2
C12
log |Z | log
1
C
6
1
2 C 2
1
C2
Z 2 10Z 1
capacitor
Z 1 10Z 2
resistor-like
Lecture 2
2.
Z2
1
Z
and Z 1
j
1
C
jC
Z12
1
Z1
1
R
1
jR
R
jC
1
R
1
pjCR 1qpjCR 1q
jCR

R
RpjCR 1q

2 R2 C 2 1
RpjCR 1q
jCR2 R
Z
p2R2 C 2 1q
R2 C j
R

2
R C ooooooooon
1
loooooooooomo
R C ooooooooon
1
loooooooooomo
Z2
Z1
pZ 2 q2 pZ 1 R2 q2
0,
Z
8, Z
at p ,
Z1
R
0
Z2

R 2
2
2.625, Fall 13
Lecture 2

R
2 R2 C 2
R C

2
1
R2 C 2
1
p
1
1
RC
1
- peak frequency
RC
Bode plot:
Equivalent circuit of an electrochemical cell

The most well-known circuit is shown below, known as Randles circuit:
R Series resistance such as ionic resistance or electronic resistance

Cdl Capacitance associated with double layer capacitance
Zf Faradaic impedance, which can be modeled by several methods shown below:
Faradaic resistance
1.
Rs Another series resistance associated with the Faradaic reaction.

Cs Pseudo capacitance associated with Faradaic reaction.
7
2.625, Fall 13
Lecture 2
2.
Rct Charge transfer resistance.

Z Warburg Impedance element, a resistance to mass transfer.
Now consider the Faradaic impedance
Z
E
dE
dt
Rs Cj
iRs
di
Rs dt
q
Cs
i
Cs
As i imax sin t, we have:
BE pR i q cos t
s max
Bt
Consider a redox reaction: O
E
dE
dt
E
E di
looBmo
Bi on dt
imax
Cs
sin t
i, r0sp0, tq, Rp0, tq
Rct
dE
dt
ne
BE dr0sp0, tq
BrOsp0,ooootqon dt
loooooomo
0
BE drRsp0, tq
BrRsp0, tq
dt
loooooomoooooon
R
drOsp0, tq
di
drRsp0, tq
Rct dt
0
R
dt
dt
Rct imax cos t need to find rOspx, tq and Rpx, tq.
Assuming semi-infinite diffusion:
rOsp0, tq rOs8
rRsp0, tq rRs8
imax
psin t cos tq
nF Ap2OO q1{2
imax
psin t cos tq
nF Ap2OR q1{2
2.625, Fall 13
Lecture 2
sp0,tq and
Plug drOdt

dE
dt :
2.625, Fall 13
r sp q into the expression of
d R 0,t
dt

imax cos t
1{2

1
0
R
? 1{2 1{2
where
nF A 2 OO
OR
Rs Rct
1{2
1
Cs
1{2
dE
dt
Zf
Rct
Rct
R
j
C
Rct
imax 1{2 sin t
p
Rs
Zf
1{2
1{2 1
looooomooooon
loooo
ooomooooooon
j
Rct R C
Rct
Rct r1{2 j1{2 s
1{2
j {Cs
j1{2
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MASSACHUSETTS INSTITUTE OF TECHNOLOGY

2.625/3.625/10.625 FALL 2013
HOMEWORK 1 (ungraded)
Solutions posted September 12, 2013
Chemical equilibrium questions warm up
Problem #1
Calculate the equilibrium constant K for ammonia synthesis reaction, N2 + 3H2 2NH3 at 298
K, and show how K related to the partial pressure of the species at equilibrium when the overall
pressure is low enough for the gases to be treated as perfect.
Problem #2
Suppose that an Iron catalyst at a particle manufacturing plant produces ammonia in the most
cost effective manner at 450C when the pressure is such that Gr for the reaction
N2(g) + 3/2H2(g) NH3(g) is equal to -500 J/mol.
(a) What pressure is needed?
(b) Now suppose that a new catalyst is developed that is most cost effective at 400C when
the pressure gives the same value of Gr. What pressure is needed when the new catalyst
is used? What are the advantages of the new catalyst? Assume that all gases are perfect
gases. Isotherms of Gr(T,P) in the pressure range 100atm p 400atm are needed to
derive the answer.
(c) Do the isotherms you plotted confirm Le Chateliers principle concerning the response of
equilibrium changes in temperature and pressure?
Hint: Le Chateliers principle: A system at equilibrium when subjected to a disturbance,
responds in a way that tends to minimize the effect of the disturbance.
Electrostatics questions warm up
Problem #3
The potential around a cylindrical shell. You have a hollow inner cylinder with radium a,
surrounded by a concentric outer cylinder with radius a2 >a1. Charges -1 and +1 per unit length
are distributed uniformly over the inner and outer cylinders, respectively. The arrangement is in a
medium with dielectric constant D.
(a) What is the potential as a function of the axial distance r?
(b) What is the capacitance per unit length of the arrangement of cylinders?
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2.625 Fall 2013

Homework 1 solutions (for practice, not graded)
1. !! = !! + !"#$ !! , but at equilibrium, !! = 0. Therefore
!! = !"#$ !! and !! = exp( !! /!")
From standard Gibbs free energies of formation for NH3, N2 and H2, !! = 2!!"
! =
!
32.8 !"/!"# , resulting in !! = 5.62 10
Equilibrium reaction constant, !! =
!
!!"
!
!
!!! !!
!
!! , where px refers to the partial pressure
of species x, and po to reference pressure

2. (a) and (b)
!
!! + !! !!!
!! = !! !!! (1)
!! ! = !! +

!
!!
!"#
! !" (2)
!! = !!"
! = 45.9 !"/!"#
!! = ! + !" + !/! ! , !"# !! = !"#$ !!!,!"#$

represents the stoichiometric coefficient for each species

!! ! = !! +

!"#$% !!!,!"#$% where
! !!
!"
!"# !
!! = 99.38 !/!"#
For ideal gases, there will be no pressure dependence on !! at constant temperature.

Thus, to see how !! depends on P, we relate !! to pressure via
!
!
!", where
!!"# !
!! ! = !! ! !
In our case, ! = 1 = 1
! is the stoichiometric coefficient
!! ! = !! ! + ! ln (3)
!!
Putting equations 1, 2 and 3 together gives us a direct relationship between !! and P,

which we may plot at two different temperatures to obtain our isotherms

At -500 J/mol,
Pressure at 450 C = 162.2 bar
Pressure at 400 C = 84.8 bar
The advantage of the new catalyst is it enables the reaction at about half the original
pressure. This will reduce the amount of pumping and compression needed to
pressurize the reaction chamber, and make ammonia synthesis cheaper.
(c) Yes. !! decreases as pressure increases, which corresponds to a shift to the right
side of the reaction, where there are fewer moles of gas. Also, since the forward
reaction is exothermic, !! goes up (corresponding to a shift to the reverse reaction) as
temperature increases, for a given pressure.
3. (a)

We may assume that the length of the cylinder, L >> a2
(All calculations done per unit length)
By Gauss Law, electric field E is defined as ! !" =
!
!"!
, where Q = 1 per unit length
Since field lines are perpendicular to our Gaussian surface, ! 2!" =

! =

!(!) =
!
!!"#!!
! (!) =
!
!!"!!
ln
!
!!
From (a), ! =
Therefore ! =
!
!!"!!
!!"!!
!"
!!
!!
, and
!
!
!!
!"
(referenced to the surface of the inner cylinder)
(b) Capacitance per unit length, C = Q/

!
!!!
ln
!!
!!
and we know Q = 1
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Fall 2013

2.625/10.625 FALL 2013
HOMEWORK 2
DUE DATE, September 19, 2013
State Your Assumptions Clearly
Problem #1
Consider two partitions of gases, one with air and one with gas emitted from an exhaust outlet.
Between, an O2 concentration sensor based on the O2 concentration cell, which is written
electrochemically as Pt/O2 (exhaust gas, pO2,eg)/ZrO2 + Y2O3/O2 (air, pO2,a)/Pt, is planted. The
overall reaction that occurs at high temperature at both of the Pt/ZrO2+Y2O3 interfaces is:
O2,exhaust O2,air
(a) Assuming constant temperature (T) and overall pressure (P), derive the expressions for the
changes in the enthalpy and entropy of moving one mole of O2 molecule from the exhaust gas
side to the air side.
(b) Write out the expression of the potential of the sensor, using potential of the air side vs. the
exhaust side, as a function of the partial pressure, pO2,eg and pO2,a. If the cell voltage reads 0.8
V, assuming pO2,a = 0.2 atm, T = 800K, what is the partial pressure of oxygen in the exhaust
gas?
O2 + 4e 2O2-
Problem #2 Short Questions

a. A steady current of 1.00 amp is passed through an electrolytic cell containing a 0.1 M aqueous
solution of CuF2 using inert graphite electrodes until 1.54 g of copper is deposited. At which
electrode is the copper deposited? (anode or cathode) and what is the half-cell reaction at the
other electrode?
b. Calculate the equilibrium constants for the following reactions at 25 oC in aqueous solutions.
(10 pt)
(a) Ni(s) + CuSO4(aq) Cu(s) + NiSO4(aq)
(b) 2H2(g) + O2(g) 2H2O(l)
c. Predict whether a reaction takes place spontaneously and explain why, and give a balanced
reaction equation.
a. Au(s) + HCl(aq)
b. Mg(s) + ZnSO4(aq)
c. Cu(s) + AuCl3(aq)
d. Sn(s)+ Al2(SO4)3(s)
d. Consider an electrochemical cell involving Zn(II) and Ni(II) and answer the following
questions:
a). Identify the anode and the cathode for spontaneous reaction
b). Write the balanced overall reaction
c). Which electrode will lose mass?
d). Which way do the electrons flow? toward Zn or Ni?
Problem #3
Considering the following electrochemical cell:
Pb/PbCl2, Hg2Cl2/Hg
At 25oC, the thermodynamic voltage of the cell is 0.4857 V and the temperature coefficient is
1.65x10-4 Volt/degree. Please calculate:
A:
(a) The maximum work available from the cell at 25oC per mole of Pb reacted.
(b) The entropy change of the cell operation.
(c) The heat adsorbed by the cell at 25oC per mole of Pb reacted when the cell is operating
reversibly.
B:
You replace the Hg electrode with an Hg-Y alloy electrode in which mole fraction XHg = 0.3.
The cell thermodynamic voltage at 25oC is found to increase by 0.0094 V. Calculate the activity

of Hg in the alloy at 25oC.

Problem #4 - Desalination
You have a desalination cell with 0.1 M solution of NaCl on each side. The activity of NaCl can
be defined as the molar concentration of NaCl divided by a reference concentration
aNaCl -
[NaCl]
[1 M]
(a) Assuming no kinetic limitations, what is the minimum applied potential required to
make one side 108 times more concentrated than the other?
(b) From the electrochemical series, devise a galvanic cell that would involve lithium
redox (Li Li + + e - ), which will provide enough electromotive force or
thermodynamic voltage for your desalination cell.
Problem #5
Efficient and economical water splitting is a key technology component of a hydrogen economy
since it utilizes the inexpensive natural resource, water, to produce hydrogen fuel.
,
(a) You are asked to do water splitting in an acidic electrolyte. Please write out the half cell
reactions at both hydrogen electrode and oxygen electrode. Please specify the cathode and anode
side. What is the overall reaction?
(b) Repeat (a) but with an alkaline electrolyte.
(c) Calculate the Gro for water splitting at standard condition (T = 298K, P=1atm).
(d) In the acidic electrolyte, derive the expression of the two half cell potential at cathode and
anode and the cell potential.
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2.625 FALL 2013
HOMEWORK 3
DUE 10/17/2013 in class (note this is a change of due date)

1. The rate constant for the first-order decomposition of N2O5 in the reaction 2N2O5 (g)
4NO2 (g) + O2 (g) is k = 7.48e-5 s-1 at 25 C.
(a) What is the half-life of N2O5?
(b) What will be the pressure, initially 300 Torr, 20s after the initiation of the reaction?
(c) How long will it take for the pressure, initially 300 Torr, to reach 100 Torr?
2. The separate adsorption isotherms for gases A and B on a certain solid obey the Langmuir
equation, and it may be assumed that the mixed or competitive adsorption obeys the
corresponding form of the equation. Gas A, by itself, adsorbs to a coverage theta of 0.03 at P
= 350 mm Hg and gas B, by itself, adsorbs a coverage of 0.03 at P = 35 mm Hg; T = 95 K in
both cases.
(a) Derive a Langmuir model expression for the competitive adsorption of gases A and B.
(b) Calculate the difference in the heat of adsorption for A and B on the solid surface.
(c) Calculate the value for coverage of A when the solid, at 95 K, is equilibrated with a
mixture of A and B such that the final pressures are 350 mm Hg each.
3. This problem will walk you through the hydrogen oxidation reaction (H2 (g) 2H+ + 2e) in
PEM fuel cells. The adsorption of CO can act as a poison, inhibiting the hydrogen oxidation
reaction by site blocking.
(a) Derive an expression using the Langmuir model for dissociative adsorption of H2 on a Pt
surface: H2 (g) 2Hads.
(b) The adsorption of CO can compete with this process. Modify your expression from 2a) to
consider the competition between the formation of COads and Hads starting from CO (g)
and H2 (g) reactants.
(c) How does this equation simplify in the limit of strong CO binding? What is the reaction
order with respect to CO (g) and with respect to H2 (g)?
(d) Plot the coverage of COads and Hads as a function of the concentration of CO, assuming a
CO adsorption energy of HCO = -1.2 eV and a dissociative H2 adsorption energy HH2 =
-0.7 eV, at pH2 = 1 bar and 300K.
(e) At what concentration of CO (in ppm) will the coverage of CO, CO, exceed that of H?
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2.625 FALL 2013
HOMEWORK 3
DUE 10/17/2013 in class
1. (a) The rate of decomposition of N2O5, !!!!! =

![!! !! ]
!"
! ![!! !! ]
!
!"
= 2!!!!!
Since we are told the reaction is first-order, !!!!! = ! !! !! ,

![!! !! ]
= 2![!! !! ]
!"
Let [!! !! ] be N
!
!"
=
!" !
2! !"
!
! = !! exp (2!")
ln 2
= 4,633 !"#!
2!
![! ! ]
If you assume that the given rate constant given applies to ! ! with [N2O5] representing all
!"
reactants, this yields a half-life of 9,270 seconds. Either will be accepted as the definition was
ambiguous.
!!/! =
(b) After 20s,
!
!!
= exp 2!. 20!"#! = 0.997, P = 0.997(300) Torr = 299.1 Torr (partial
pressure of N2O5).
![! ! ]
If you assume that the given rate constant given applies to ! ! with [N2O5] representing
!"
all reactants, the partial pressure of N2O5 after 20s is 299.6 Torr.
!
!"" !"##
(c) ! =
= exp 2!. ! ; solve for t
!"" !"##
!
ln 3
!!""!"## =
= 7,344 !"#! = 2 ! 2 !"#
2!
![! ! ]
If you assume that the given rate constant given applies to ! ! with [N2O5] representing
!"
all reactants, the time to reach a partial pressure of N2O5 of 100 Torr is 14,700 seconds.
2. (a) Competitive adsorption for the mixture of A and B, starting from Langmuir isotherm for
A and B:
!
!! !
= !!"#,! ! !!"#,! =
!
!! !! !
= !
= !!"#,! !! [!!"## ]
! !!
!
!! ! !!
= !
!!"#
!
!!"##
!!"#
!
![!! ]
[!!"# ]
!
= !!"#,! ! !!"#,! =
=
=
!!"#
!! (1 !)
!! 1 ! [!! ]
!! [!!"## ]
1 !
= !!"#,! !! [!!"## ]
where [So] is the concentration of total sites, [Aads] is the concentration of the sites
occupied by A, [Bads] is the concentration of the sites occupied by B, [Sfree] is the
concentration of free sites.
[So ] = [Sfree ] + [A ads ] + [Bads ]

= [Sfree ] + K ads,A PA [Sfree ] + K ads,B PB [Sfree ]
= [Sfree ] (1 + K ads,A PA + K ads,B PB )
(b) Apply the Langmuir isotherm for A:
!!"#,!
!
= !!"#,! !
1 !
!
0.03
=
=
= 0.067
350!! !"
! !"# (1 !)
760!! !" 1 0.03
Apply the Langmuir isotherm for B:
!!"#,! =
!
= !!"#,! !
1 !
!
0.03
=
= 0.67
35!! !"
! !"# (1 !)
760!! !" 1 0.03
We know that
!!"# ! (
!!"#
)
!
!(
!!!"#
)
!
Assuming A and B are ideal gases, where the adsorption entropy from gas to solid is the
same for all gases; we can take the ratio of adsorption constants of A and B
!!"#,!
!!"#,!
ln
!"# (
!!!"#,!
!"
!!!"#,!
!"# (
)
!"
!!"#,!
!!"#,! (!!"#,! )
=
!!"#,!
!"
!!"#,! !!"#,! = !" ln
!!"#,!
!!"#,!
= 1.82 !"/!"#
(c)

where PA = PB = 350 mmHg*(1atm/760 mmHg) = 0.46

3. CO poisoning in PEM fuel cells
12 $!$%!"%(#! $!####."!!(
"!#")!+
<"0"<6
<601 "01-18/6222<6
!8;83>83*#$!##!("#!! <-148/4?82
$##!#""!#"!#(" $##!+
17-428/48<
"*
#$"

12
12 !#"%(848*&!8"#!#!#"!$"*
""$##8=!#"!#,
!*

'%"

##""#!*#
==7==
8

!

""!"#!!&#!"##8"#!#!!"-8&#!"##",
12 "#%%$"#(""$"!#6,8/
16,:#
966
2*#"#&+

(e) Setting the equations for coverage of H equal to coverage of CO, one obtains a
pressure for CO gas which can be converted to ppm using the ideal gas equation
~0.03 ppm CO
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2.625 FALL 2013
HOMEWORK 4
DUE 10/17/2013 in class (with homework 3)
1. The initial rate of the reaction 2A + 2B ---> C + D is determined for different initial
conditions, with the results listed in the following table:
Run #
1
2
3
4
[A]0, M
0.266
0.133
0.266
0.133
[B]0, M
0.185
0.370
0.370
0.185
Initial rate, M/s

1.35 X 10-3
6.75 X 10-4
2.70 X 10-3
3.35 x 10-4
Find the rate law and rate constant for this reaction.
2. (a) Show that for a first-order homogeneous reaction, A
A is 1/kf .
B, the average lifetime of
(b) A form of radioactive astatine, useful for the treatment of some types of
cancer, is an particle emitter with a half-life of 7.21 hr. If 0.100 mg of astatine
is given to a person at 8 a.m., how much astatine will remain at 10 p.m.?
3. Consider the reaction: 2A + B 3C. In one experiment it was found that at 300 K the
rate constant is 0.268 L/(mol.s). A second experiment showed that at 450 K, the rate
constant was 1.138 L/(mol.s). Determine the activation energy for the reaction.
4. Consider the elementary reaction: A + BC AB + C
(a) Express the rate law (define rA) using the Arrhenius equation.
(b) Now utilize transition state theory (TST), where an activated molecule is formed
during the reaction at the transition state between forming products from reactants:
We can express the rate of reaction as the product of the frequency of the activated
complex crossing the barrier and the concentration of the transition state complex,
with the transition state molecule and reactants in pseudo equilibrium at the top of the
energy barrier. Write the expression for the equilibrium constant of KC#.
(c) Express the rate law as a function of T, a change in free energy, and the
concentration of reactants. Draw a diagram specifying this change in free energy as a
function of reaction coordinate, and draw how the curve would change with the use of
a catalyst.
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HOMEWORK 4
DUE 10/17/2013 in class

1. This is an initial rates problem with more than on species present as a reactant. We
must therefore isolate the effect of each of the reactants' concentrations on the overall rate
of reaction. Runs number 3 and 1 have the same concentration of A but the concentration
of B is half. The rate of the reaction is halved too, so the reaction is first order in B. Runs
number 3 and 2 have the concentration of B the same but the concentration of A halves.
The rate is four times less under these conditions so the reaction is second order in A.
Thus the rate law is
rate = k[A]2[B]
The rate constant may be evaluated with any set (row) of data. Try run #3
2.70 x 10-3 M/s = k(0.266 M)2(0.370 M)
k = 0.103 M-2 s-1
As a check, lets use run #4
3.35 x 10-4 M/s = k(0.133 M)2 (0.185 M)
k = 0.102 M-2 s-1
2. (a)
For first order reactions,
dnA
dt
= -kf nA
nA (t) = nA,O exp (-kf t), where nA,O is the number of

moles of A at time, t = 0.
First we obtain a probability distribution of A with time, by normalizing:
1 = i a . nA,O exp (-kf t)
a=
!:
nA,O
, where a is the normalization constant
Average lifetime is therefore the expectation of the probability distribution:

kf
T =<t >= i t
X _A,O exp(-kf t) dt
_A,O
o
1
T=
kf
(b) Half-lives are constant for first order reactions: ln2 = kthalf
thalf = 7.21 hr, so k = ln2/7.21 hr = 0.0961 hr-1
ln(mfinal /minitial) = -kt
ln(mfinal/0.100 mg) = -(0.0961 hr-1)(14 hr)
mfinal = 0.026 mg astatine remaining
3. Compare the two rate constants to solve for Ea.

k300 = Ae -Ea/RT , similar for k450
k4S0
1
Ea 1
In
=
k300
I 300 450
Ea = 10.8 kJ
4. (a)
(b)
(c) Combining with

gives
where q is overall the partition function per unit volume and is the product of
translational, vibration, rotational and electric partition functions (this part is not
necessary for credit). To put it more simply:
-rA = kF#[A][BC]exp(-Gfo/RT)
where k F#= kBT/h
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HOMEWORK 5
DUE DATE, November 5, 2013
State all assumptions clearly

Problem #1
In most cases, the currents for individual processes are additive, that is, the total current, it, is
given as the sum of the currents for different electrode reactions (i1, i2, i3). Consider a solution
with a Pt working electrode immersed in a solution of 0.3 M HBr and 1mM K3Fe(CN)6. Assume
the following exchange current densities:
H+/H2 jo = 10-3 A/cm2, o = 0 V
Br2/Br- jo = 3 10-3 A/cm2, o = 1.0874 V
Fe(CN)63-/ Fe(CN)64- jo = 4 10-5 A/cm2, o = 0.361 V
Calculate and plot the current density-potential curve for (a) each process and (b) this system
scanning from the anodic background limit to the cathodic background limit; please use a y-scale
of 100 A/cm2. Assume = 0.5 and no mass transport limitations. (c) What do you expect would
happen if the concentration of K3Fe(CN)6 was increased 10-fold?
Problem #2
Consider the electrode reaction O + ne- R. Under the conditions that CR* =CO*=5mM, ko =
10-6cm/s, =0.4 and n=1.
a. Calculate the exchange current density jo=io/A in A/cm2
b. Draw a current density vs. overpotential curve for this reaction for anodic and cathodic
currents up to 600 A/cm2.
c. Draw log(absolute value of j) vs. overpotential for the current ranges in (b).
Problem #3
Consider a single proton exchange membrane fuel cell operated at 70 C with pure H2 and pure
O2 inputs at 150 kPa, in which Pt nanoparticles supported on carbon are used as the
electrocatalyst for hydrogen reduction and oxygen reduction. The anode and cathode electrode
geometric areas (projected) are 3.5 cm2. The exchange current densities for the rate determining
steps of oxygen reduction and hydrogen oxidation on Pt nanoparticles are 6x10-11A/cm2 and
2x10-3A/cm2, respectively. Assume that the roughness factor (Areal,Pt/Ageo) for the electrodes is
350.
1) Calculate the equilibrium fuel cell voltage under the operating conditions.
2) Develop an analytical expression that relates the fuel cell operating voltage to the current
density obtainable from the fuel cells by considering activation overpotentials in the
anode and in the cathode. Plot the effect of activation overpotentials to the fuel cell
voltage loss as a function of current density in mA/cm2 in the range from 0 to 2A/cm2.
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EXAM I (OPEN BOOK, in class)
October 4, 2011
Please state your assumptions clearly and show your analysis step by step
Short Questions (total 30 points) feel-good questions
Question 1. Which of the following is the strongest oxidizing agent? (5 pt)
A. H2O2 in acid
B. MnO4- in acid
C. MnO4- in base
D. CrO42- in acid
Please state your rationale.
Question 2. In an electrolytic cell to generate H2 from water splitting, which statement is always
true? (5 pt)
A. H2 evolves at the cathode
B. Protons migrates from anode to cathode
C. O2 evolves at the cathode
D. The electrode for H2 evolution is the positive electrode
Question 3. A steady current of 1.00 amp is passed through an electrolytic cell containing a
0.1 M aqueous solution of CuF2 using inert graphite electrodes until 1.54 g of copper is
deposited. (10 pt)
A. At which electrode is the copper deposited? (anode or cathode) and what is the half-cell
reaction at the other electrode? (5 pt)
B. How many minutes does the current flow to obtain this deposit? (5 pt)
Question 4. Calculate the equilibrium constants for the following reactions at 25 oC in aqueous
solutions. (10 pt)
(a) Zn(s) + CuSO4(aq) Cu(s) + ZnSO4(aq)
(b) 2H2(g) + O2(g) 2H2O(l)
Problem #1 (10 points)

Extraction of lithium from LiFePO4, first reported by Goodenough and co-workers in 1997,1
results in the formation of FePO4 ((1-x) LiFePO4 + xFePO4, where the solid solution of
LixFePO4 does not exist). The following figure shows the charge and discharge profiles of
LiFePO4 in an Li/FePO4 cell:1
FePO4LiFePO4LiClO4 in PC:DME(1:1)Li
[Ref]: (1) J.B. Goodenough et al., JES, 144 (4), 1997

The Electrochemical Society, Inc. All rights reserved. This content is excluded from our Creative Commons license.
For more information, see http://ocw.mit.edu/help/faq-fair-use/.
Source: Padhi, A. K., K. S. Nanjundaswamy, et al. "Phospho.olivines as Positive-Electrode Materials for Rechargeable
Lithium Batteries." Journal of the Electrochemical Society 144, no. 4 (1997): 1188-94.
(a) What are the half-cell reactions at the two electrodes and the whole-cell reaction? (2 pt)
(b) Please compute the gravimetric energy (in Wh/gLiFePO4) of the cell (by only considering
the weight of LiFePO4) (4 pt)
(c) Please explain why lithium removal from LiFePO4 exhibits a voltage plateau but not a
slopping voltage profile? Hint: develop your rational using Nernst equation (4 pt)
Molecular weight of LiFePO4 is 157.75 g/mol

One promising approach to increase the energy density of lithium batteries involves replacing the
intercalation compound with an oxygen electrode forming a lithium-oxygen (Li-O2) battery.
Here are two types of Li-air batteries, aqueous and non-aqueous systems. For aqueous Li-O2
batteries, the lithium metal is protected by a ceramic lithium ion conductor (LiSICON).
Courtesy of Macmillan Publishers Limited. Used with permission.

Source: Bruce, Peter G., Stefan A. Freunberger, et al. "Li-O2 and Li-S batteries
with high energy storage." Nature materials 11, no. 1 (2012): 19-29.
(a) Please write down the oxygen half-cell reaction and the net reaction of an Li-O2 battery (right
graph), where the oxygen electrode is in an alkaline electrolyte (i.e, LiOH). What is the
equilibrium cell voltage if the cell operates at pH=14 and 1 atm O2 for the oxygen electrode
and at aLi+=1 for the lithium electrode (Li Li+ + e-)? (5 pt)
(b) Please write down the oxygen half-cell reaction and the net reaction for an Li-O2 battery in an
acidic electrolyte (i.e., HClO4). What is the equilibrium cell voltage if the cell operate at 1M
HClO4, 1atm O2 and at aLi+=1 for the lithium electrode (Li Li+ + e-)? (5 pt)
(c) Please write down the oxygen half-cell reactions and the net reaction for an Li-O2 battery in
non-aqueous electrolytes (i.e., LiClO4) in the left graph. What is the equilibrium cell voltage
(1atm O2 and 1M LiClO4) if the final product is Li2O2 and Li2O at 298 K, respectively? (10
pt)
(d) Consider an Li-O2 battery in non-aqueous electrolytes (i.e., LiClO4) in the left graph, what is
the equilibrium cell voltage (0.2 atm O2 and 1M LiClO4) if the final product is Li2O2 at
333K? (10 pt)

Pourbaix diagrams are graphical representations of thermodynamic and electrochemical
equilibria occurring in aqueous systems. They are thus the electrochemical analogues of the
chemical phase stability diagram. In the Pourbaix diagram of Aluminum, the species
participating in the various chemical and electrochemical equilibria are the solids Al and Al2O3
and ions Al3+ and AlO2-.
You are given:
Gfoo(kJ/mol)
Al(s)
0
1608.9
Al2O3(s)
Al3+(aq)
481.2
AlO2 (aq)
839.8
H2O(l)
237.1
H+(aq)
(a) Write down the half-cell reaction between Al3+ and Al and plot it in a Pourbaix diagram for
[Al3+] = 10-5 M and 1 M. (10 pt)
(b) Write down the half-cell reaction between Al2O3 and Al and plot in the Pourbaix diagram for
PO2 of 10-5 atm and 1 atm. (10 pt)
(c) Plot the chemical reaction of Al3+ + 2H2O AlO2- + 4H+ in the Pourbaix diagram, and
compute at what PH value, you would find [Al3+] = [AlO2-]? (10 pt)
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EXAM I Solution
Question 1. Which of the following is the strongest oxidizing agent? (5 pt)

A. H2O2 in acid
B. MnO4- in acid
C. MnO4- in base
D. CrO42- in acid
Please state your rationale.
Answer: A
The oxidizing ability of an oxidizing agent is directly related to the ability to get electrons from
other substance. Therefore, the strongest oxidizing agent has the highest reversible reduction
potential.
A. H2O2 in acid:
H2O2 + 2H+ + 2e- 2H2O, Eo = 1.776 V
B. MnO4- in acid:
MnO4- + 8H+ + 5e- Mn2+ + 4H2O, Eo = 1.507 V
C. MnO4- in base:
MnO4- + 2H2O + 3e- MnO2 + 4OH-, Eo = 0.595 V
D. CrO42- in acid:
CrO42- + 8H+ + 3e- Cr3+ + 4H2O, Eo = 1.35 V
Since H2O2 in acid has the highest reduction potential, it is the strongest oxidizing agent.
Question 2. In an electrolytic cell to generate H2 from water splitting, which statement is always
true? (5 pt)
A. H2 evolves at the cathode
B. Protons migrates from anode to cathode
C. O2 evolves at the cathode
D. The electrode for H2 evolution is the positive electrode
Answer: A
B: This is not true in alkaline solutions.
C: O2 evolves at the anode.
D: H2 evolves at the negative electrode.
Question 3. A steady current of 1.00 amp is passed through an electrolytic cell containing a
0.1 M aqueous solution of CuF2 using inert graphite electrodes until 1.54 g of copper is
deposited. (10 pt)
A. At which electrode is the copper deposited? (anode or cathode) and what is the half-cell
reaction at the other electrode? (5 pt)
B. How many minutes does the current flow to obtain this deposit? (5 pt)
Answer:
A: The copper is deposited at the cathode (Cu2+ + 2e- Cu)
At the anode, we need to find the oxidation reaction:
Because 2F- F2 + 2e- -2.866V
2H2O O2 + 4H+ + 4e- -1.23V > -2.866V (water is easier to be oxidized than F-)
So the reaction at anode is 2H2O O2 + 4H+ + 4eB: Faradays law
i t
m
(1.0) t
1.54
,
Zr F 63.5 2 96485 63.5
t = 78 min
Question 4. Calculate the equilibrium constants for the following reactions at 25 oC in aqueous
solutions. (10 pt)
(a) Zn(s) + CuSO4(aq) Cu(s) + ZnSO4(aq)
(b) 2H2(g) + O2(g) 2H2O(l)
Answer:
(a) The reaction can be written into two half cell reactions
Zn Zn2+ + 2e-
0.762V
Cu2+ + 2e- Cu
0.342V
Overall: Zn + Cu2+ Zn2+ + Cu 1.104V
G oo
r Z r F (2)(96485)(1.104) 213.04
K= exp(
kJ
mol
-G oo
213040
r
) exp(
) 2.2 1037
8.314 298
RT
(b) The reaction can be written into two half cell reactions
2H2(g) 4H+ + 4eO2(g) + 4H+ + 4e- 2H2O(l)
0.0V
1.229V
Overall: 2H2(g) + O2(g) 2H2O(l) 1.229V

G oo
r Z r F (4)(96485)(1.229) 473.3
K= exp(
kJ
mol
-G oo
473300
r
) exp(
) 9.22 1082
8.314 298
RT
Problem #1
(a) What are the half-cell reactions at the two electrodes and the whole-cell reaction? (2 pt)
(b) Please compute the gravimetric energy (in Wh/gLiFePO4) of the cell (by only considering the
weight of LiFePO4) (4 pt)
(c) Please explain why lithium removal from LiFePO4 exhibits a voltage plateau but not a
slopping voltage profile? Hint: develop your rational using Nernst equation (4 pt)
Molecular weight of LiFePO4 is 157.75 g/mol
Answer:
LiFePO4 FePO4 + Li+ + e-
(a) Positive electrode:

Negative electrode:
Li+ + e- Li
Overall:
LiFePO4 FePO4 + Li
(b) Energy = charge*voltage

Gravimetric charge =
Zr F
(1) F
C
611.63 170 mAh/g

M.W. 157.75
g
Assume an average potential of 3.5 V

E = 170 10-3
Ah
3.5 V = 0.595 Wh/g
g
(c) According to Nernst equation
aLiFePO4
RT
ln(
)
Zr F aLi aFePO4
For a two-phase reaction, LiFePO4, FePO4 are all pure substances (no mixing).
Hence, aLiFePO4 aFePO4 1
In addition, lithium is also pure substance, aLi 1
aLiFePO4
RT
) o , which is not a function of lithium content.
ln(
Zr F aLi aFePO4
Therefore, LiFePO4 exhibits a voltage plateau upon lithium removal from LiFePO4.
Problem #2
(a) Please write down the oxygen half-cell reaction and the net reaction of an Li-O2 battery (right
graph), where the oxygen electrode is in an alkaline electrolyte (i.e, LiOH). What is the
equilibrium cell voltage if the cell operates at pH=14 and 1 atm O2 for the oxygen electrode and
at aLi+=1 for the lithium electrode (Li Li+ + e-)? (5 pt)
Answer:
Positive electrode (cathode): O2(g) + 4e- + 2H2O(l) 4OH-(aq)

Negative electrode (anode): 4Li(s) 4Li+(aq) + 4e-
0.401V
3.045V
Net reaction: 4Li(s) + O2(s) + 2H2O(l) 4Li+(aq) + 4OH-(aq) 3.446V

o
cell cell
2
4
PO 1 1
RT 1 11
RT aO2 aH2O aLi
RT
o
o
ln( 4
) cell
ln( 2 - ) cell
ln(
) 3.446 V ,
aLi+ aOH4F
4F 1 [OH ]
4F
11
assuming ideal gas for oxygen (aO2 = PO2), and aOH- = [OH-] = 1M (pH = 14).
aLi(s) = aH2O(l) = 1 due to pure substance.
(b) Please write down the oxygen half-cell reaction and the net reaction for an Li-O2 battery in an
acidic electrolyte (i.e., HClO4). What is the equilibrium cell voltage if the cell operate at 1M
HClO4, 1atm O2 and at aLi+=1 for the lithium electrode (Li Li+ + e-)? (5 pt)
Answer:
Positive electrode (cathode): O2(g) + 4H+(aq) + 4e- 2H2O(l)

Negative electrode (anode): 4Li(s) 4Li+(aq) + 4eNet reaction: 4Li(s) + 4H+(aq) + O2(g) 2H2O(l) + 4Li+(aq)
o
cell cell
1.229V
3.045V
4.274V
4
4
+ 4
RT 1 1 1
RT aO2 aH+ aLi
RT PO2 [H ] 1
o
o
ln( 4
)
ln(
) cell
ln(
) 4.274 V ,
cell
2
aLi+ aH2O
4F
1 1
4F
1 1
4F
assuming ideal gas for oxygen (aO2 = PO2), and aH+ = [H+] = 1M
aLi(s) = aH2O(l) = 1 due to pure substance.
(c) Please write down the oxygen half-cell reactions and the net reaction for an Li-O2 battery in
non-aqueous electrolytes (i.e., LiClO4) in the left graph. What is the equilibrium cell voltage
(1atm O2 and 1M LiClO4) if the final product is Li2O2 and Li2O at 298 K, respectively? (10 pt)
Answer:
If the final product is Li2O2

Positive electrode (cathode): O2(g) + 2Li+ + 2e- Li2O2(s)
Negative electrode (anode): 2Li(s) 2Li+ + 2eNet reaction: 2Li(s) + O2(g) Li2O2(s)
cell
o
cell
2
2
RT aO2 aLi
RT PO2 aLi
RT 1 1
o
o
o
ln(
) cell
ln(
) cell
ln( ) cell
, assuming ideal gas
2F
aLi2O2
2F
aLi2O2
2F
1
for oxygen (aO2 = PO2), and aLi+ = [Li+] = 1M (1M LiClO4).

aLi(s) = aLi2O2(s) = 1 due to pure substance.
o
cell
oo
oo
oo
-G or (G f, Li2O2(s) 2 G f, Li(s) G f, O2(g) ) (570900 0 0)
2.96 V
2F
2F
2(96485)
If the final product is Li2O

Positive electrode (cathode): O2(g) + 4Li+ + 4e- 2Li2O (s)
Negative electrode (anode): 4Li(s) 4Li+ + 4eNet reaction: 4Li(s) + O2(g) 2Li2O (s)
o
cell cell
4
4
RT aO2 aLi
RT PO2 aLi
RT 1 1
o
o
o
ln( 2
) cell
ln( 2
) cell
ln( ) cell
, assuming ideal gas
4F
aLi2O
4F
aLi2O2
4F
1
for oxygen (aO2 = PO2), and aLi+ = [Li+] = 1M (1M LiClO4).

aLi(s) = aLi2O(s) = 1 due to pure substance.
o
cell
oo
oo
oo
-G or (2 G f, Li2O(s) 4 G f, Li(s) G f, O2(g) ) (561200 0 0)
2.91 V
4F
4F
4(96485)
(d) Consider an Li-O2 battery in non-aqueous electrolytes (i.e., LiClO4) in the left graph, what is
the equilibrium cell voltage (0.2 atm O2 and 1M LiClO4) if the final product is Li2O2 at 333K (10
pt)
Answer:
Positive electrode (cathode): O2(g) + 2Li+ + 2e- Li2O2(s)
Negative electrode (anode): 2Li(s) 2Li+ + 2eNet reaction: 2Li(s) + O2(g) Li2O2(s)
cell (333K)
o
cell
o
(333K)
cell
2
2
RT aO2 aLi
RT PO2 aLi
o
(333K)
ln(
) cell (333K)
ln(
)
2F
2F
aLi2O2
aLi2O2
R(333K) 0.2 1
8.314(333) 0.2 1
o
ln(
) cell
(333K)
ln(
)
2F
1
2(96485)
1
o
(333K)-0.0231 V
cell
assuming ideal gas for oxygen (aO2 = PO2), and aLi+ = [Li+] = 1M (1M LiClO4).
aLi(s) = aLi2O2(s) = 1 due to pure substance.
o
We need to find cell
(333K)
o
(333K) =
cell
- G or (333K) - (H or (333K) - TSor (333K))
2F
2F
H or (333K) - H oo
r (298K) =
T2
T1
T2
Cp dT = (Cp,Li2O2 - Cp,O2 - 2Cp,Li

) (T2 - T1 ) = (70.63 - 29.4 - 2 24.8)(333 - 298) = -292.95
Sor (333K) - Soo

r (298K) = C p
T1
J
mol
dT
T
333
J
= (C p,Li2O2 - C p,O2 - 2C p,Li ) ln 2 = (70.63 - 29.4 - 2 24.8) ln(
)= -0.9295
T
T1
298
mol K
J
mol

J
Sor (333K) = Soo

r (298K) 0.9295
K mol
H or (333K) = H oo
r (298K) 292.95
oo
oo
oo
H oo
r (298K) = H f, Li 2 O2(s) 2 H f, Li(s) H f, O2(g) ( 634300) 2(0) 0 634300
oo
oo
oo
Soo
r (298K) = SLi 2 O2(s) 2 S Li(s) SO2(g) 56.48 2(29.1) 205.2 206.92
o
(333K) =
cell
J
mol K
J
mol
- G or (333K) - (H or (333K) - TSor (333K)) ( 634593 - (333)( 207.85)
2.93 V
2F
2F
2(96485)
o
cell (333K) = cell
(333K)-0.0231 V=2.93 - 0.0231 = 2.9069 V
Problem #3
(a) Write down the half-cell reaction between Al3+ and Al and plot it in a Pourbaix diagram for
[Al3+] = 10-5 M and 1 M. (10 pt)
(b) Write down the half-cell reaction between Al2O3 and Al and plot in the Pourbaix diagram for
PO2 of 10-5 atm and 1 atm. (10 pt)
(c) Plot the chemical reaction of Al3+ + 2H2O AlO2- + 4H+ in the Pourbaix diagram, and
compute at what PH value, you would find [Al3+] = [AlO2-]? (10 pt)
Answer:
(a)
Al3+ + 3e- Al(s), o = -1.662 V
RT aAl3+
RT [Al3+ ]
ln(
) 1.662
ln(
) 1.662 1.97 102 log[Al3+ ]
3F
3F
1
aAl(s)
,assuming aAl3+ = [Al3+] and aAl(s) = 1 due to pure substance.
[Al
[Al
3+
3+
]=10-5
1.662 1.97 102 log(105 ) 1.7605 V
1.662 1.97 102 log(1) 1.662 V

]=1
(b)
Al2O3 + 6H+ + 6e- 2Al + 3H2O
Coupled with SHE: 3H2 6H+ + 6eOverall reaction: Al2O3 +3H2 2Al + 3H2O
KJ
G oo
r 3( 237.1) 0 ( 1608.9) 897.3
mol
-G oo
-897300
r

1.55 V
6F
6F
6
RT aAl2O3(s) a[H+ ]
o
r r
ln(
) 1.55 0.059pH volts
aAl(s) aH3 2O
6F
o
r
This potential of this reaction is not a function of PO2.
(c)
Al3+ + 2H2O AlO2- + 4H+
KJ
G oo
r ( 839.8) 2( 237.1) ( 481.2) 115.8
mol
This is a chemical reaction, no electron is involved

G or G oo
r RTln
[AlO 2 - ]
[H + ]4
0 (chemical equilibrium)
[Al3+ ]
[AlO 2 - ] [H + ]4
115800 = -(8.314) (298) (2.303) log
[Al3+ ]
[AlO 2 - ]
20.29 4pH
log
[Al3+ ]
if [Al3+ ] = [AlO2 - ] pH = 5.07
0.0
-
3+
[Al ]/[AlO ] = 1
2
E (volts)
-0.5
-1.0
-1.5
Al2O3
3+
[Al ]=1M
3+
-5
[Al ]=10 M
-2.0
Al
-2.5
7
pH
9 10 11 12 13 14
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2.625/10.625 FALL 2012
EXAM 1
SHORT PROBLEMS
1. Consider two electrodes made of Li and Cu placed in an alkaline electrolyte and
connected to a voltmeter. The system is in electrochemical equilibrium. Assign each
statement as either true or false (5 points):
(a)
(b)
(c)
(d)
The potential at the Li electrode is higher than the potential at the copper electrode
Cu is the positive electrode
Phase potential is equal across the whole cell
Li is the cathode
3. (a) Write down the half cell and overall cell reactions for an ethanol fuel cell operating in
alkaline electrolyte. Assume
2 =
, =
[ ]
[ ]0
, 2 = 1, 2 = 1, [ ]0 = 1.
(b) What is the cathode potential at pH = 10 if the cell is operating in dry air?
(B) What is the equilibrium constant for the following reaction at 298 K and 1atm
pressure:
2NaCl + 2H2O Cl2 + 2H2 + 2NaOH
What is the physical implication of your result?
(c) Identify the metal(s), with corresponding metal ions in solution, that can plate
spontaneously vs SHE.
a. Ba/Ba2+
b. Pt/Pt2+
c. Ru/Ru2+
d. Ca/Ca2+
Does the driving force for metal plating increase or decrease as pH increases? Please
show why using a Pourbaix diagram.
PROBLEMS
1. In an Li-ion battery, Li ions are inserted (intercalated) into the positive electrode on
discharge or extracted (deintercalated) from the positive electrode on charge. The
positive electrode consists of a host crystal structure with lattice sites that can
accommodate storage of the Li ions. This problem considers the thermodynamics of
Li intercalation during discharge into an electrode material, LixMO2 (or alternatively
into LiMPO4), where x is the fraction of lithiated sites in MO2 or MPO4, 1-x is the
fraction of unlithiated MO2 or MPO4 sites, and x varies between 0 and 1 during
discharge.
Assume that intercalation occurs slowly enough that the system can be considered to be
at equilibrium. Consider the following thermodynamic properties for the positive
electrode.
which describes the entropy per site in the lattice associated with displacing MO2 sites by
LiMO2 sites during discharge, and
hi = ho x(1 x)
which describes the enthalpy per site in the lattice associated with interactions between
intercalated phases within the electrode.
The discharge voltage of the positive electrode is given by
= 0
()
We assume the negative electrode is lithium metal, and therefore the positive electrode voltage is
referenced to V vs. Li.
(a) Develop an expression for the Gibbs free energy, g, per site as a function of x and
given constants.
(b) What is the chemical potential, , as a function of x? What is the cell voltage, , as a
function of x?
(c) Consider that the positive electrode behaves as a solid solution during discharge.
Assuming that the enthalpic contributions, h, to the free energy, g, are negligible such
that ho = 0 (i.e., the free energy is determined predominantly by the entropy of
mixing). What equation results? Does this look familiar? Assuming a value of 0 = 4
V vs. Li and kBT/e = 0.1, sketch (x) for the solid solution case below.
(d) Now assume that the enthalpic contributions are significant, such that kBT/e = 0.1 and
ho = 2kBT, which is representative of a two-phase intercalation process where mixing
between phases is not thermodynamically favorable. Sketch the shape of as a
function of x assuming 0 = 3.6 V below.
(e) Match your voltage profiles to the experimental data of two positive electrode
materials shown below. Which positive electrode material exhibits solid solution
behavior and which exhibits two-phase behavior? Briefly describe the physical
mechanisms happening during discharge for these two materials.
source unknown. All rights reserved. This content is excluded from our Creative Commons
license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
7.
The sodium-sulfur (NAS) battery is an emerging energy storage technology that uses sodium and
sulfur for electrode active materials and -alumina ceramics for the electrolyte. Fig. 1 shows the
schematic of a NAS battery cell at 300 oC. (Dunn, B. et al, Science, 2011) During discharge,
sodium is oxidized and the sodium ions pass through the -alumina electrolyte to the positive
electrode where they react with sulfur forming various sodium polysulfide species (i.e., Na2Sx).
Fig. 1. Schematic of the Na/S battery. (Source: Dunn, B. et al, Science, 2011)
American Association for the Advancement of Science. All rights reserved. This content is excluded from our Creative
Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
Source: Dunn, Bruce, Haresh Kamath, et al. "Electrical Energy Storage for the Grid: A Battery of Choices." Science 334,
no. 6058 (2011): 928-35.
(a) There are three reaction stages during discharge. First, the S(l) is reduced to Na2S5(l),
which is immiscible with S(l) at 300 oC (two separated liquids). Second, the Na2S5(l) can
be reduced to Na2S3(l) via a solid-solution mechanism. Lastly, the Na2S3(l) can be further
reduced to Na2S2(l) via a two-phase transition. Sketch the Na-S cell electromotive force
(Emf) as a function of state-of-discharge in the following graph. (Gf o,300 degC of Na2S5(l) =
-400 kJ/mol, Gf o,300 degC of Na2S3(l) = -370 kJ/mol, Gf o,300 degC of Na2S2(l) = -138.7 kJ/mol).
(b) A sodium-air battery can be constructed if we replace the sulfur with dry air (with carbon
matrix) and decrease the temperature from 300 oC to 25 oC, as shown in Fig. 2.
Please write out three half-cell reactions at the positive electrode forming NaO2(s),
Na2O2(s), and Na2O(s), respectively. Compute the equilibrium cell potentials versus
Na+/Na in 0.5 M NaPF6 (in a nonaqueous solvent) if dry air is used at 25 oC. (Hf o,o of
NaO2 = -260.7 kJ/mol, Sf o,o of NaO2 = 115.9 J/mol K, Hf o,o of Na2O2 = -510.9 kJ/mol, Sf
o,o
of Na2O2 = 95 J/mol K, Hf o,o of Na2O = -414.2 kJ/mol, Sf o,o of Na2O = 75.1 J/mol K,
Sf o,o of O2 = 205.2 J/mol K, Sf o,o of Na = 51.3 J/mol K 2).
(c) Knowing the heat capacities of NaO2, Na2O2 and Na2O are comparable (75 J/mol K),
calculate the corresponding equilibrium cell potentials versus Na+/Na in presence of
oxygen ion conductor if dry air is used at 300 oC. Please explain the physical origin of the
changes in the potential as a function of temperature, and please explain the physical
origin to the differences in the redox potentials of Na-S and Na-oxygen (for NaO2 and
Na2O2) at a given temperature. Assume cp,O2 = 29.4 J/mol K and cp,Na = 28 J/mol K. (10
points).
Note that we get a negative sign owing to a typo in one of the provided free energies. The correct value is
actually 1.75 V, but full marks will be given for this result
2
Note that entropies of formation of Na and O were omitted; full marks will be given per stated assumptions.
6
(d) Which reaction has the highest gravimetric energy (Wh) per kg of reactants under
standard temperature and 300 oC based on the Gibbs free energy of reactions given in (b)
and (c)? Please explain/show why (5 points)
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2.625/10.625 FALL 2012
EXAM 1
SHORT PROBLEMS
1. Consider two electrodes made of Li and Cu placed in an alkaline electrolyte and
connected to a voltmeter. The system is in electrochemical equilibrium. Assign each
statement as either true or false (5 points):
(a)
(b)
(c)
(d)
The potential at the Li electrode is higher than the potential at the copper electrode
Cu is the positive electrode
Phase potential is equal across the whole cell
Li is the cathode
Solution:
A. False; the Li redox reaction is -3.04 V lower than the hydrogen redox reaction
B. True
C. False; phase potential changes at the interfaces between Li and electrolyte and Cu and
electrolyte.
D. False
2. The production of metallic aluminum from aluminum ore in an electrolytic cell occurs as
follows:
22 3() 4() + 32()
Estimate the cost of production of 1 kg of Al under standard conditions in a 3 104 cm2

cell, assuming:
The cell operates at 0.3 V above the minimum applied cell voltage at a current
of 0.85 A/cm2
Electricity costs $0.15/kWh
23
= 1582.3 /
Solution:
First, we calculate the thermodynamic cell potential.
=
= (4
+ 3 2
) 223
= 3164.6
3164.6 /
1296485/
= 2.73
= 2.73 + 0.3 = 3.03
Next we calculate amount of time required to produce 1kg of Al

, =
, molar weight (MW) of Al = 26.98 g/mol
1000 96,485 / 3
= 420 = 7.01
3 104 0.85 26.98/
, =
Total energy required = 3 104 0.85 420 3.03 3.66 = 9.02

$0.15
Total cost = 9.02 = $1.35/kgAl
3. (a) Write down the half cell and overall cell reactions for an ethanol fuel cell operating in
alkaline electrolyte. Assume
2 =
, =
[ ]
[ ]0
, 2 = 1, 2 = 1, [ ]0 = 1.
(b) What is the cathode potential at pH = 10 if the cell is operating in dry air?
Solution:
(a)
Anode: C2H5OH + 12OH- 2CO2 + 9H2O + 12eCathode: 3O2 + 6H2O + 12e- 12OHOverall: C2H5OH + 3O2 2CO2 + 3H2O
(b)
12
ln 3 6

02 20
20 = 1, 2 = 0.21, = [ ]
At pH = 10, pOH = 14 10 = 4
4 = log10
= 104
8.314 298
(104 )12
= 0.403
ln
= 0.63
12 96485
0.213
(B) What is the equilibrium constant for the following reaction at 298 K and 1atm
pressure:
2NaCl + 2H2O Cl2 + 2H2 + 2NaOH
What is the physical implication of your result?
Solution:
= ln
2
220
= 2
= 2(379.7) 2(237) 2(384.1) = 482.8 /
= = 2.34 1085
This low equilibrium constant (<<1) means that the reaction does not go to completion
spontaneously
(c) Identify the metal(s), with corresponding metal ions in solution, that can plate
spontaneously vs SHE.
a. Ba/Ba2+
b. Pt/Pt2+
c. Ru/Ru2+
d. Ca/Ca2+
Does the driving force for metal plating increase or decrease as pH increases? Please
show why using a Pourbaix diagram.
Solution:
Metals with reduction potentials higher than SHE will plate spontaneously.
Ba/Ba2+ has = -2.912 V so will not plate spontaneously
Pt/Pt2+ has = 1.18 V so will plate spontaneously
Ru/Ru2+ has = 0.455 V so will plate spontaneously
Ca/Ca2+ has = -2.868 V so will not plate spontaneously
3
The driving force for metal plating increases as pH increases. As pH increases, while
the potential for metal ion reduction stays constant, the potential for hydrogen
oxidation reduces and so the potential difference between the two reactions and
hence the driving force - also increases.
0.4
0.2
0.0
-0.2
-0.4
2H+ + 2e- ---> H2
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
-1.8
-2.0
10
12
14
pH
PROBLEMS
1. In an Li-ion battery, Li ions are inserted (intercalated) into the positive electrode on
discharge or extracted (deintercalated) from the positive electrode on charge. The
positive electrode consists of a host crystal structure with lattice sites that can
accommodate storage of the Li ions. This problem considers the thermodynamics of
Li intercalation during discharge into an electrode material, LixMO2 (or alternatively
into LiMPO4), where x is the fraction of lithiated sites in MO2 or MPO4, 1-x is the
fraction of unlithiated MO2 or MPO4 sites, and x varies between 0 and 1 during
discharge.
Assume that intercalation occurs slowly enough that the system can be considered to be
at equilibrium. Consider the following thermodynamic properties for the positive
electrode.
which describes the entropy per site in the lattice associated with displacing MO2 sites by
LiMO2 sites during discharge, and
hi = ho x(1 x)
4
which describes the enthalpy per site in the lattice associated with interactions between
intercalated phases within the electrode.
The discharge voltage of the positive electrode is given by
= 0
()
We assume the negative electrode is lithium metal, and therefore the positive electrode voltage is
referenced to V vs. Li.
(a) Develop an expression for the Gibbs free energy, g, per site as a function of x and
given constants.
SOLUTION:
g( x) = h ( x) Ts( x)
g ( x) = ho x(1 x) + k BT ( x ln( x) + (1 x) ln(1 x) )
(b) What is the chemical potential, , as a function of x? What is the cell voltage, , as a
function of x?
SOLUTION:
G
= = ho (1 2 x) + k BT (ln x ln(1 x) )
x T ,P
x
1 x
= ho (1 2 x) + k BT ln
( x) = o
ho
kT x
(1 2 x) B ln
e
e
1 x
(c) Consider that the positive electrode behaves as a solid solution during discharge.
Assuming that the enthalpic contributions, h, to the free energy, g, are negligible such
that ho = 0 (i.e., the free energy is determined predominantly by the entropy of
mixing). What equation results? Does this look familiar? Assuming a value of 0 = 4
V vs. Li and kBT/e = 0.1, sketch (x) for the solid solution case below.
SOLUTION:
( x) = o
k BT x
ln
e
1 x
This is the Nernst equation assuming aLiMO2 =[LiMO2]=x and aMO2=[MO2]=1-x. Note that
kBT/e = RT/F.
(d) Now assume that the enthalpic contributions are significant, such that kBT/e = 0.1 and
ho = 2kBT, which is representative of a two-phase intercalation process where mixing
between phases is not thermodynamically favorable. Sketch the shape of as a
function of x assuming 0 = 3.6 V below.
SOLUTION:
(e) Match your voltage profiles to the experimental data of two positive electrode
materials shown below. Which positive electrode material exhibits solid solution
behavior and which exhibits two-phase behavior? Briefly describe the physical
mechanisms happening during discharge for these two materials.
source unknown. All rights reserved. This content is excluded from our Creative
SOLUTION:
The solid solution describes the behavior of LiCoO2 on discharge, where entropic effects
of mixing govern the thermodynamics. The enthalpic effect is negligible (Li ions do not
strongly feel the presence of other Li ions in the solution). In contrast, LiFePO4 has a
stronger contribution from the enthalpic term owing to immiscibility between the two
phases LiFePO4 and FePO4, exhibiting a discharge plateau characteristic of two-phase
processes.
7.
The sodium-sulfur (NAS) battery is an emerging energy storage technology that uses sodium and
sulfur for electrode active materials and -alumina ceramics for the electrolyte. Fig. 1 shows the
schematic of a NAS battery cell at 300 oC. (Dunn, B. et al, Science, 2011) During discharge,
sodium is oxidized and the sodium ions pass through the -alumina electrolyte to the positive
electrode where they react with sulfur forming various sodium polysulfide species (i.e., Na2Sx).
Fig. 1. Schematic of the Na/S battery. (Source: Dunn, B. et al, Science, 2011)
American Association for the Advancement of Science. All rights reserved. This content is excluded
from our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
Source: Dunn, Bruce, Haresh Kamath, et al. "Electrical Energy Storage for the Grid: A Battery of
Choices." Science 334, no. 6058 (2011): 928-35.
(a) There are three reaction stages during discharge. First, the S(l) is reduced to Na2S5(l),
which is immiscible with S(l) at 300 oC (two separated liquids). Second, the Na2S5(l) can
be reduced to Na2S3(l) via a solid-solution mechanism. Lastly, the Na2S3(l) can be further
reduced to Na2S2(l) via a two-phase transition. Sketch the Na-S cell electromotive force
(Emf) as a function of state-of-discharge in the following graph. (Gf o,300 degC of Na2S5(l) =
-400 kJ/mol, Gf o,300 degC of Na2S3(l) = -370 kJ/mol, Gf o,300 degC of Na2S2(l) = -138.7 kJ/mol).
Solution:
In the first reaction stage, S is reduced to Na2S5:
5 + 2 2 5
25 5 2
=
=
= 2.07
2
In the third reaction stage, Na2S3 is reduced to Na2S2:
22 3 + 2 32 2
322 223 2
=
= 1.68 1
Between the first and third reaction stages, varies according to the state of discharge:
4
4
2 5 + + + 10 5
3
3
3
Note that we get a negative sign owing to a typo in one of the provided free energies. The correct value is
actually 1.75 V, but full marks will be given for this result
(b) A sodium-air battery can be constructed if we replace the sulfur with dry air (with carbon
matrix) and decrease the temperature from 300 oC to 25 oC, as shown in Fig. 2.
Please write out three half-cell reactions at the positive electrode forming NaO2(s),
Na2O2(s), and Na2O(s), respectively. Compute the equilibrium cell potentials versus
Na+/Na in 0.5 M NaPF6 (in a nonaqueous solvent) if dry air is used at 25 oC. (Hf o,o of
NaO2 = -260.7 kJ/mol, Sf o,o of NaO2 = 115.9 J/mol K, Hf o,o of Na2O2 = -510.9 kJ/mol, Sf
o,o
of Na2O2 = 95 J/mol K, Hf o,o of Na2O = -414.2 kJ/mol, Sf o,o of Na2O = 75.1 J/mol K,
Sf o,o of O2 = 205.2 J/mol K, Sf o,o of Na = 51.3 J/mol K 2).
Solution:
In dry air, aO2 = 0.2
(1) + + 2 + 2

00 =
= 2.26
Note that entropies of formation of Na and O were omitted; full marks will be given per stated assumptions.
= 00
= 00
= 00
ln 1 2
= 2.26
1
+ 2
(2) 2 + + 2 + 2 2 2

=
= 2.32
ln 222
= 2.32
1
+ 2
(3) 4 + + 2 + 4 22

=
= 1.95
ln 0.50.2 = 2.20
ln 0.52 0.2 = 2.28
ln 4 2
= 1.95 4 ln 0.54 0.2 = 1.922
1
+ 2
(c) Knowing the heat capacities of NaO2, Na2O2 and Na2O are comparable (75 J/mol K),
calculate the corresponding equilibrium cell potentials versus Na+/Na in presence of
oxygen ion conductor if dry air is used at 300 oC. Please explain the physical origin of the
changes in the potential as a function of temperature, and please explain the physical
origin to the differences in the redox potentials of Na-S and Na-oxygen (for NaO2 and
Na2O2) at a given temperature. Assume cp,O2 = 29.4 J/mol K and cp,Na = 28 J/mol K. (10
points).
For NaO2, () = + 298 () = 255.36 /
() = + 298
= 129.1 /( )
= = 181.9 /

0 =
= 1.89
12
1
00
=
ln 1
= 1.89
ln
= 2.00
1
+ 2
0.5 0.2
For Na2O2, () = + 298 () = 513.76 /
() = + 298
= 219.6 /( )
= = 387.9 /

0
=
= 2.01
122
1
00
= 0
ln 2
=
2.01
ln
= 1.936
+ 12
2 0.52 0.2
For Na2O, () = + 298 () = 809.9 /
10
() = + 298
216.3 /( )
= = 685.9 /

0
=
= 1.78
1
= 00
ln 4
= 1.78
ln 4
= 1.672
1
+ 2
4 0.5 0.2
At higher temperatures, all redox potentials decrease because of the negative entropic
contribution to the free energy from condensing O2 gas in a solid i.e. since G = H
TS, if S is negative, any increase in temperature will reduce the amount of free energy
available to do work.
For the one and two-electron reactions, the redox potentials of the Na-oxygen reaction at
300 C (2.00 and 1.94 V) are slightly higher on average than the redox potentials of Na-S
at the same temperature (2.07 and 1.75 V). This is because O has a slightly higher
electronegativity than S and thus a slightly higher affinity for electrons from Li oxidation.
(d) Which reaction has the highest gravimetric energy (Wh) per kg of reactants under
standard temperature and 300 oC based on the Gibbs free energy of reactions given in (b)
and (c)? Please explain/show why (5 points)
, =
At 298 K, Na2O = 3859.3 J/g, Na2O2 = 5640.7 J/g, NaO2 = 6743 J/g
At 573 K, Na2O = 3508.5 J/g, Na2O2 = 4789 J/g, NaO2 = 5866 J/g
Na2O reaction is highest at all temperatures.
11
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MASSACHUSETTS INSTITUTE OF TECHNOLOGY 2.625/10.625 FALL 2013

EXAM 1
SHORT PROBLEMS
1. Hydrogen fuel can be produced by the electrolysis of water:

The D0E target cost of H2 is $3.10/kg. You design a cell that operates in standard
conditions (25 C, 1 atm), with pH2 and p02 of 1 atm. Electricity costs
$0.15/kWh, and your wiring can only handle a current of 200 A. What is the
allowable voltage input which just reaches this cost goal, and how does this
compare to the thermodynamic voltage?
2. Identify whether the metal(s), with corresponding metal ions in solution, would
spontaneously displace Zn.
a. Cu/Cu2+
b. Cr/Cr2+
c. Ni/Ni
2+
d. Does the driving force for Zn dissolution increase or decrease as pH

increases?
PROBLEMS
3. A battery can be formed by reacting Zn with air, using an alkaline electrolyte.
a. Write the equations at the anode, cathode, and overall for the discharge of
this galvanic cell, assuming a product of Zn0.
b. What potential would I obtain if I tested the cell in air (p02 = 0.2) at 25 C?
c. How many liters of air (p02 = 0.2) must a Zn-air cell "breathe" in to produce 1
Ah at 25 C? Assume 1 mole of gas occupies 22.4 L, and the partial pressure is
proportional to the volume fraction.
d. Zn-air batteries are often used in devices such as hearing aids due to their
high gravimetric energy density (Wh/kg). What is the energy density per kg
product at 25 C? The molecular weight of Zn is 65.38 g/mol, and of 0 is
15.9994 g/mol.
e. A battery could also be formed from the Zn-S system. If Hf00ZnS = -206
kJ/mol and Sf00ZnS = 57.7 J/mol, what is the energy density per kg ZnS at 25
C? The molecular weight of Zn is 65.38 g/mol, and of S is 32.0655 g/mol.
f. How does the gravimetric energy density of ZnS compare to that of ZnO7
4. Chlorine is used to disinfect (read: oxidize germs) in pool water. Attached is a
partially completed Pourbaix diagram for Chlorine in water, where we plot the
equilibrium lines for the following reactions on the attached diagrams:
Cl2 + 2e 2Cl
HClO + H+ + e Y Cl2 + H2O
HClO ClO + H+
O2 + 4H+ + 4e 2H2O
2H+ + 2e H2
EOr = 1.36 vs. SHE
EOr = 1.61 vs. SHE
pKa = 7.54
EOr = 1.229 vs. SHE
EOr = O vs. SHE
We leave dashed the lines which may or may not determine the stable species.
a. Draw in an additional equilibrium line on the attached diagram 4a, labeling
the intercept and slope, for the reaction:

and label the stable specie(s) in each region.
b. On attached diagram 4b, draw the equilibrium lines if concentration of Cl
was reduced, and the pressure of H2(g) increased. (Redraw your line from
part a, as well as at a lower concentration of Cljhigher pH2 if applicable)
c. What specie is the oxidant in swimming pool water (pH 7.4)7
5. LijFeS2 AA batteries offer a higher operating voltage than traditional alkaline AA
batteries. In these batteries, Li intercalates during discharge into an electrode
material, LiyFeS2, where y is the number of lithiated sites in FeS2, and goes from O
to 2 during discharge.
Assume that intercalation occurs slowly enough that the system can be
considered to be at equilibrium. Consider the following thermodynamic
properties for the positive electrode:
SLiyFeS2
which describes the entropy per site in the lattice associated with displacing
FeS2 sites by LiyFeS2 sites during discharge, where x is the mole fraction of total
Li sites occupied, and the enthalpy per site (regular solution model) is described
as:
hi = ho x(1- x)
and the discharge voltage of the positive electrode is given by:

a. What is the chemical potential in terms of the Li stoichiometry, y?
b. What is the cell voltage as a function of Li stoichiometry, y?
c. Assume that the enthalpic contributions are significant, such that kBT/e
(equivalent to RT/F) = 0.1 and ho = 2kBT, which is representative of a twophase intercalation process where mixing between phases is not
thermodynamically favorable. Sketch in your booklet the shape of E as a
function of y assuming E0 = 2.0 V vs. Li.
d. If the cell is discharged slowly enough, a secondary reaction can be observed:
2Li + Li2FeS2-->2Li2S + Fe
Sketch in your booklet the shape of E as a function of capacity below, and
note the location of 2.0 V relative to your curve.
Name
Please fold in half and insert into your exam answer booklet.
4. a)
b)
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Fall 2013

2.625 FALL 2013
EXAM #2, TAKE HOME
RELEASE DATE: October 22, 2013
DUE DATE: October 24, 2013
State all assumptions clearly and work on this exam independently
Problem #1: 40 points, 10 points each part
The cyclic voltammogram of polycrystalline Pt in 0.5M H2SO4 of Figure 1 shows the
adsorption of Hads and desportion of Hads in the voltages in the range from 0V and ~0.35V
vs. Reversible Hydrogen Electrode (RHE) upon cathodic and anodic scans at a voltage
sweep rate of 100mV/s, respectively. The horizontal axis is the sweeping voltage vs.
RHE and the vertical axis shows the current. Further lowering the sweep rate can only
lower the current output but does not modify the general features (such as the peak
positions and relative peak heights) found in the hydride region. Assume adsorption of
Hads atoms on Pt follows Langmuir isotherm. We here focus on the cathodic sweep into
the potential region of H2 evolution. We only consider the weakly HA1 (0.1 V) and
strongly HA2 (0.25V) adsorbed sites in this problem. Please clearly state your
assumptions and show step by step the following relationship between the current and
voltage in the hydride region:
where F is Faradays constant; now is the mole of available sites for the weakly adsorbed
species; nos is the mole of available sites for the strongly adsorbed species; w and s is
the coverage of weakly and strongly adsorbed species, respectively; is the sweep rate.
Hints: (a) write out the adsorption, charge transfer and the overall half-cell reaction, (b)
relate the half-cell voltage to the pressure of hydrogen gas in equilibrium with the
electrode, (c) relate the pressure of hydrogen to the coverage of adsorbed hydrogen
species, and (d) relate the current to the change of coverage of adsorbed hydrogen as a
function of time
Figure 1: Cyclic voltammogram of polycrystalline Pt in 0.5M H2SO4

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Problem #2: 30 points, 5 points each part

Ammonia synthesis (N2 + 3H2 2NH3) is a reaction of great technological importance.
For the reaction to proceed, both N2 and H2 must be adsorbed dissociatively on the
surface. This problem will consider only a small segment of this reaction, the N
hydrogenation reaction (N+HNH), which plays an important role.
(a) Assume the rate for the N hydrogenation reaction (N+HNH) is first order.
Write an Arrhenius expression for this reaction.
(b) For what values of [N] and [H] will the rate of hydrogenation be maximized, and
what does this imply about the free energy of dissociative adsorption of N2 and
H2?
(c) Express the ratio of coverages for N and H with respect to the free energy of
dissociative adsorption using the Langmuir adsorption equation.
(d) Below are the activation barriers to dissociation (Ea) and chemisorption energies
(Ead, the difference in free energy between the clean surface + gas phase and the
adsorbed state) in eV for N2 and H2 on numerous metal surfaces, obtained from
CatApp. Plot Ea vs Ead for both N2 and H2 dissociative adsorption on all the
close-packed surfaces. The relationship between these thermodynamic parameters
is the crux of the Bronsted-Evans-Polanyi principle. Briefly explain how this
assumption is used in establishing the volcano plots of question 4.
Table 1: Activation barriers (Ea) and chemisorption energies (Ead) in eV, for N2 2N*
and H2 2H*. Obtained from CatApp, http://suncat.slac.stanford.edu/catapp/
Metal
Ea (N2)
Ead (N2)
Ea (H2)
Ead (H2)
Ru (0001)
1.9
-0.58
0
-1
Ru (0001) step 0.4
-0.82
0
-1.1
Pd (111)
3.9
2
0.12
-0.79
Cu (111)
4.8
3.4
0.63
-0.15
Rh (111)
2.1
-0.25
0.25
-0.66
(e) Given these tabulated values, which surface do you expect to be most active for
hydrogenation? Explain why in one sentence.
(f) Compare Ea and Ead of the most active surface to all those plotted in part d;
where are these values in relation to the line of best fit for the other surfaces?
Provide or two sentences considering the implication.
Problem #3: 10 points
How is the strength of chemisorption of an adsorbate affected by the coordination
number of surface metal atoms to which it is bonded? Discuss this in the context of CO
adsorption onto step and terrace sites on the Pt surface. See reference: Hammer, B. et al.
Catalysis Letters 46 (1997) 31 - 35
Problem #4: 20 points
For aqueous ORR electrocatalysis in acid in Figure 2a (Norskov et al. JPCC 2004) and in
basic solutions in Figure 2b (Lima et al. JPCC 2007), the ORR activity can be governed
by the oxygen binding to the catalyst surface, forming a volcano shape as a function of
oxygen binding.
American Chemical Society. All rights reserved. This content is

excluded from our Creative Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.
Source: Nrskov, Jens Kehlet, Jan Rossmeisl, et al. "Origin of the
Overpotential for Oxygen Reduction at a Fuel-Cell Cathode." The
Journal of Physical Chemistry B 108, no. 46 (2004): 17886-92.
American Chemical Society. All rights reserved. This

content is excluded from our Creative Commons license.
For more information, see http://ocw.mit.edu/help/faqfair-use/.
Source: Lima, F. H. B., J. Zhang, et al. "Catalytic Activity
-d-Band Center Correlation for the O2 Reduction Reaction
on Platinum in Alkaline Solutions." The Journal of Physical
Chemistry C 111, no. 1 (2007): 404-0.
Figure 2. (a) Trends in ORR activity in an acidic electrolyte plotted as a function of

calculated oxygen binding energy (Norskov et al. JPCC 2004). (b) Trends in ORR
activity (kinetic current ik at 0.8 VRHE) in a basic electrolyte plotted as a function of
calculated metal d-bend center (d-F, relative to the Fermi level) (Lima et al. JPCC
2007).
Discuss a likely reaction model for each electrolyte (10 points), explain why the activity
of oxygen reduction reaction exhibits volcano relationship with regard to the binding of
oxygen on metal surfaces (5 points), and discuss how the surface electronic structure
(such as d band center relative to the Fermi level) of metals can influence the binding of
oxygen (5 points). (Hints: based on the reaction mechanism proposed by you, identify the
plausible rate-determining step of ORR on each branch of the volcano.
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2.625 FALL 2013
EXAM #2, TAKE HOME SOLUTIONS
RELEASE DATE: October 22, 2013
DUE DATE: October 24, 2013

1. The cyclic voltammogram of polycrystalline Pt in 0.SM HzS04 shows the adsorption
of Hads and desportion of Hads in the voltages in the range from 0V and 0.3SV vs.
Reversible Hydrogen Electrode (RHE) upon cathodic and anodic scans at a voltage
sweep rate of 100mVIs, respectively. The horizontal axis is the sweeping voltage vs.
RHE and the vertical axis shows the current. Further lowering the sweep rate can
only lower the current output but does not modify the general features (such as the
peak positions and relative peak heights) found in the hydride region. Assume
adsorption of Hads atoms on Pt follows Langmuir isotherm. We here focus on the
cathodic sweep into the potential region of Hz evolution. We only consider the
weakly HA1 (0.1 V) and strongly HAz (0.zSV) adsorbed sites in this problem. Please
clearly state your assumptions and show step by step the following relationship
between the current and voltage in the hydride region:
where F is Faradays constant; now is the mole of available sites for the weakly adsorbed
species; nos is the mole of available sites for the strongly adsorbed species; w and s is the
coverage of weakly and strongly adsorbed species, respectively; is the sweep rate.
Hints: (a) write out the adsorption, charge transfer and the overall half-cell reaction, (b)
relate the half-cell voltage to the pressure of hydrogen gas in equilibrium with the
electrode, (c) relate the pressure of hydrogen to the coverage of adsorbed hydrogen
species, and (d) relate the current to the change of coverage of adsorbed hydrogen as a
function of time.
(a) Write out the adsorption, charge transfer and the overall half-cell reactions
Volmer reaction (charge transfer): 2H+ + 2e- 2Had
Tafel reaction (chemical reaction): 2Had H2
Overall half-cell reaction: 2H+ + 2e- H2,g
(b) Relate the half-cell voltage to the pressure of hydrogen gas in equilibrium with the
electrode
The equilibrium potential from Nernst equation for the half-cell reaction: (aH+=1, Po =
1atm):
where PH2 can be found from Langmuir dissociative isotherm.

(c) Relate the pressure of hydrogen to the coverage of adsorbed hydrogen species.
From the lecture notes, the Langmuir isotherm for dissociative adsorption is:
(d) Relate the current to the change of coverage of adsorbed hydrogen as a function of time
where no is the number of moles of available sites for H adsorption.
z. Ammonia synthesis (N2 + 3H2 2NH3) is a reaction of great technological

importance. For the reaction to proceed, both N2 and H2 must be adsorbed
dissociatively on the surface. This problem will consider only a small segment of this
reaction, the N hydrogenation reaction (N+HNH), which plays an important role.
(a) Assume the rate for the N hydrogenation reaction (N+HNH) is first order.
Write an Arrhenius expression for this reaction.
Rate = AeEa/RT[N][H]
(b) For what values of [N] and [H] will the rate of hydrogenation be maximized?
Equal
What does this imply about the free energy of dissociative adsorption of N2 and
H2 ?
Equal (assuming pressures are comparable, but the influence of pressure is only
to the power rather than exponential)
(c) Express the ratio of coverages for N and H with respect to the free energy of
dissociative adsorption using the Langmuir adsorption equation.
[N]/[H] = exp{(Ead,N - Ead,H )/2kT}*(PN/PH)^1/2
(d) Below are the activation barriers to dissociation (Ea) and chemisorption energies
(Ead, the difference in free energy between the clean surface + gas phase and the
adsorbed state) in eV for N2 and H2 on numerous metal surfaces, obtained from
CatApp. Plot Ea vs Ead for both N2 and H2 dissociative adsorption on all the
close-packed surfaces. The relationship between these thermodynamic parameters
is the crux of the Bronsted-Evans-Polanyi principle. Briefly explain how this
assumption is used in establishing the volcano plots of question 4.
Table 1: Activation barriers (Ea) and chemisorption energies (Ead) in eV, for N2 2N*
and H2 2H*. Obtained from CatApp, http://suncat.slac.stanford.edu/catapp/
Metal
Ea (N2)
Ead (N2)
Ea (H2)
Ead (H2)
Ru (0001)
1.9
-0.58
0
-1
Ru (0001) step 0.4
-0.82
0
-1.1
Pd (111)
3.9
2
0.12
-0.79
Cu (111)
4.8
3.4
0.63
-0.15
Rh (111)
2.1
-0.25
0.25
-0.66
Ea (eV)
Dark points are the Ru stepped surface used in part f.
Because the activation energy scales with the change in energy for adsorption,
which is related to the binding energy of a given adsorbate by considering the
difference in free energy between a clean surface + gas and the adsorbed state,
we can describe the rate of reaction by the binding energy of a species and not
worry about the difficult calculation of the transition state.
4
3.S
3
z.S
z
1.S
1
0.S
0
-0.S 0
-1
-1.S
Nz
Hz
z
dEads (eV)
(e) Given your tabulated values, which surface do you expect to be most active for
hydrogenation? Explain why in one sentence.
Ru (0001) stepped. The difference in adsorption energies is small so there will be

comparable coverage.
(f) Compare Ea and Ead of the most active surface to all those plotted in part d;
where are these values in relation to the line of best fit for the other surfaces?
Provide one or two sentences considering the implication.
It lies off the line. Ead are more similar and thus [N] and [H] will be more
comparable; similarly, the activation energy of N2 dissociation is smaller than
expected based on the BEP relation for close-packed surfaces. Creating steps
breaks the scaling relation.
3. How is the strength of chemisorption of an adsorbate affected by the coordination
number of surface metal atoms to which it is bonded? Discuss this in the context of
CO adsorption onto step and terrace sites on the Pt surface.
References
Hammer, B. et al. Catalysis Letters 46 (1997) 31 - 35
In general, the lower the coordination number of the site of adsorption, the higher the d band
center and therefore the higher the CO chemisorption strength. This is because from the tight
binding model, the band will narrow as the coordination number is reduced, and will
therefore have to shift up to keep the same number of unoccupied states. The location of the
CO antibonding orbitals depends on the distance to the d-band center. When it is higher,
antibonding states are unoccupied. Thus undercoordinated sites bind stronger to CO.
4. For aqueous ORR electrocatalysis in acid in Figure 2a (Norskov et al. JPCC 2004)
and in basic solutions in Figure 2b (Lima et al. JPCC 2007), the ORR activity can
be governed by the oxygen binding to the catalyst surface, forming a volcano
shape as a function of oxygen binding.
4
American Chemical Society. All rights reserved. This content is

excluded from our Creative Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.
Source: Nrskov, Jens Kehlet, Jan Rossmeisl, et al. "Origin of the
Overpotential for Oxygen Reduction at a Fuel-Cell Cathode." The
Journal of Physical Chemistry B 108, no. 46 (2004): 17886-92.
American Chemical Society. All rights reserved. This

content is excluded from our Creative Commons license.
For more information, see http://ocw.mit.edu/help/faqfair-use/.
Source: Lima, F. H. B., J. Zhang, et al. "Catalytic Activity
-d-Band Center Correlation for the O2 Reduction Reaction
on Platinum in Alkaline Solutions." The Journal of Physical
Chemistry C 111, no. 1 (2007): 404-0.
Figure 2. (a) Trends in ORR activity in an acidic electrolyte plotted as a function of

calculated oxygen binding energy (Norskov et al. JPCC 2004). (b) Trends in ORR
activity (kinetic current ik at 0.8 VRHE) in a basic electrolyte plotted as a function of
calculated metal d-bend center (d- F, relative to the Fermi level) (Lima et al. JPCC
2007).
Discuss a likely reaction model for each electrolyte (10 points), explain why the activity
of oxygen reduction reaction exhibits volcano relationship with regard to the binding of
oxygen on metal surfaces (5 points), and discuss how the surface electronic structure
(such as d band center relative to the Fermi level) of metals can influence the binding of
oxygen (5 points). (Hints: based on the reaction mechanism proposed by you, identify the
plausible rate-determining step of ORR on each branch of the volcano.
MIT OpenCourseWare
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Fall 2013

2.625 FALL 2013
EXAM #3, TAKE HOME
RELEASE DATE: November 21, 2013
DUE DATE: November 26, 2013
Problem #1 (40 points, 5 points each part)
Table 1: Polarization data from a single H2/O2 fuel cell at 70 C and 150 kPa
Current density j
Area-specific ohmic
(A/cm2electrode)
Cell voltage E (V)
resistance (Ohm cm2)
0.02
0.922
0.067
0.05
0.895
0.065
0.1
0.874
0.064
0.2
0.849
0.063
0.4
0.818
0.062
0.6
0.794
0.061
0.8
0.772
0.061
1
0.753
0.061
1.19
0.734
0.061
1.49
0.708
0.061
Consider the tabulated polarization data from a single H2/O2 fuel cell at 70 C and 150
kPa and please complete the following:
a) Compute the reversible cell voltage
b) Calculate the ohmic-corrected cell voltage and plot both this and the raw cell
voltage as a function of jcell on a linear scale
c) Create a Tafel plot using ohmic-corrected cell voltage
d)
C
alculate jo for the H2/O2 fuel cell from the Tafel plot normalized to (1) geometric
electrode/cell area and (2) true surface area of Pt (assume a roughness factor that
gives 350 cm2Pt/cm2geo,electrode)
e) The exchange current density for the rate determining steps of hydrogen oxidation
on Pt nanoparticles is 2x10-3A/cm2Pt. Considering both the forward and reverse
reactions, plot 1H + /H2 as a function of the current densities jgeo (assume a roughness
factor that gives 350 cm2Pt/cm2geo/electrode).
f) Compare and discuss the physical significance of jo determined from the H2/O2 fuel
cell relevant to the kinetics of H2 electrode and O2 electrode based on what you have
learned in class
g) The oxygen diffusivity in humidified air at 70C is about 0.264 cm2/s, while in
water at 70C it is 0.0000482 cm2/s. Assume the dissolved oxygen concentration in
liquid water is 5x10-4 M. Calculate the limiting current in both situations (where the
fuel cell is humidified and flooded), assuming the diffusion layer near the electrode
can be treated as a stagnant region 50 microns thick.
h)
Plot the concentration overpotential as a function of the current densities jgeo for
the humidified case.

Consider the following two voltammograms collected from rotating disk electrode
measurements, which show the one electron transfer ferri/ferrocyanide reaction in a
supporting NaOH electrolyte at two different concentrations. The concentration of
potassium ferrocyanide is 20 mol/m3 and the electrode is a disk with 3 mm radius. The
diffusion constant of potassium ferrocyanide when [NaOH]500mol/m3 = 6.455 x10-10 m2/s
and when [NaOH]3000mol/m3 = 3.764 x10-10 m2/s. Please use and show a Koutecky-Levich
plot to determine the kinematic viscosity of the electrolyte for each condition.
American Chemical Society. All rights reserved. This content is excluded from our Creative
Source: Bourne, John R., Peter Dell'Ava, et al. "Densities, Viscosities, and Diffusivities in
Aqueous Sodium Hydroxide-Potassium Ferri-and Ferro-Cyanide Solutions." Journal of Chemical
and Engineering Data 30, no. 2 (1985): 160-3.
References
- Bard and Faulkner chapter 9.3
- Recitation Demo #3
- Bourne et. al J. Chem. Eng. Data, 1985, 30 (2), pp 160163
Consider the following two voltammograms collected from rotating disk electrode
measurements, which show oxygen reduction currents in two different electrolyte
solvents (PC and Pyr14TFSI) at 50 mV/s and different electrode rotation rates between
300 and 2700 rpm.
Reference
- Herranz, J., Garsuch, A., Gasteiger, H.A., Journal of Physical Chemistry C, 2012,
116, 19084-19094
PC
Pyr14TFSI
American Chemical Society. All rights reserved. This content is excluded from our Creative Commons license. For more
information, see http://ocw.mit.edu/help/faq-fair-use/.
Source: Herranz, Juan, Arnd Garsuch, et al. "Using Rotating Ring Disc Electrode Voltammetry to Quantify the Superoxide
Radical Stability of Aprotic LiAir Battery Electrolytes." The Journal of Physical Chemistry C 116, no. 36 (2012): 19084-94.
Estimate the concentration of oxygen in each electrolyte as well as the kinetic current.
Assume a one-electron transfer reaction and a diffusivity of oxygen of 25x10-6 cm2/s in
PC and 8.8x10-6 cm2/s in Pyr14TFSI (salt used is 0.2 M TBATFSI). Kinematic viscosity
of PC is 2.6x10-2 cm2/s and 54x10-2 cm2/s for Pyr14TFSI, and electrode area is 0.196
cm2.
For the following Randles circuit of an electrochemical cell, please i) derive an equation
for the complex impedance Z(), specifying the Real and Imaginary parts of Z(); ii)
sketch the Nyquist and Bode Impedance plots you would expect to see from this cell.
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2.

625 - Electrochemical Systems

Lecture 2 - Thermodynamics Overview

II. Review 1st and 2nd laws of thermodynamics

For a closed system of constant mass,

i. internal energy is constant: IU = 0

Subbing in T dS IS for Q and rearranging, we have

For reversible processes, IS = 0, so T dS = dU + P dV . This is Gibbs fundamental equation.

Thus, a system approaches equilibrium by minimizing G such that

We can dene the partial dierentials in the above equation as follows:

A. Comparing this to the expression for dG above,P

E. For an ideal gas, we dene the partial pressure as:

vii. Thus, at we can dene the chemical equilibrium condition: Gr = nRT ln Ka

Figure 6: Example plot of ln Ka vs.

. ln Ka varies approximately linearly with

2.625 - Electrochemical Systems

Lecture 3 - Chemical Potential and Equilibrium

Example reactions and concentration cells

Chemical Potential and Equilibrium

V. Nernst Equation for ideal reacting gases

E. The reaction potential, Er is ultimately a function of a temperature dependent term, system

VI. Chemical Equilibrium vs. Electrochemical Equilibrium

Chemical Potential and Equilibrium

VII. Concentration Cells

PH2 (108 atm)

Consider the reaction O2 + 4H+ + 4e 2H2 O, where EO

EO2 ,H+ /H2 O = Ecatho

Chemical Potential and Equilibrium

Ecell = Ecathodic Eanodic = 0.409V > 0

This reaction will occur spontaneously. Iron is not stable.

2.625 - Electrochemical Systems

Lecture 4 - Electrochemical Cells

Electrochemical series of half cell reactions (P o , T o , oO/R )

Figure 1: Electrochemical series of copper, hydrogen, and zinc

Nernst Voltage of this reaction is :cell = oR +

ln aoR is the Nernst half cell potential for O/R

Example- Consider H2 concentration cell

assuming ideal gas for H2 and P =1atm aH2 =

cell = cathode anode =

II. Pourbaix Diagrams

activity of solution species

a. Consider hydrogen electrode potential vs. pH

activity coefficient = 1 for ideal solution

Recall that ln x = 2.303 log x and pH = log[H + ]

At room temperature, 298 K, Hydrogen electrode potential as f (pH, PH2 ):

O2 ,H + /H2 = oO2 ,H + /H2 +

O2 ,H + /H2 = 1.229 + 0.0148 log PO2 0.059pH

m weight of reactant or product (g)

Example: To make H2 at 1g/s, what current is needed?

105 C/s = 105 A

Large current needed (1g/s 105 A) due to large F

Assuming $0.15/kWh, electricity cost of $7/kg for H2 .

2.625 - Electrochemical Systems

Lecture 8 - Kinetics of Chemical and Electrochemical Reactions

Kinetics of Chemical and Electrochemical Reactions

Figure 2: Overpotential losses as a function of

Figure 3: Overpotential losses as a function of

Figure 4: Illustration of ohmic overpotential

Figure 5: Lithium battery potential as a function

Kinetics of Chemical and Electrochemical Reactions

Kinetics (a) limited

Figure 6: Current as a function of potential for a kinetically limited device.