2016-07-07

Chapter 17
Spontaneous Change: How Far?

Understanding and applying the second law of

thermodynamics.
Understanding the relationship between rG and
K and the dependence of equilibrium constants on
temperature.

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Lecture Outline
Spontaneous Direction of Change and Equilibrium
Entropy and Second Law of Thermodynamics
Standard Molar Entropy of Substances, S
Entropy Changes and Spontaneity
Gibbs Free Energy and Spontaneity
rG and Ecell for Voltaic Cell Reactions
Dependence of Equilibrium Constants on Temperature
Dependence of Equilibrium Vapour Pressures on
Temperature

Spontaneous Direction of Change and

Equilibrium
Spontaneous refers to the direction of reaction that would take a reaction
mixture closer to a state of chemical equilibrium.
To predict whether a process is spontaneous, we can use a thermodynamic
property called entropy (S).
The concept of entropy is built on the idea that spontaneous change results in
dispersal of energy.
Entropy (S) is a measure of the lack of order resulting from dispersal of energy
and matter.
q qrev = the heat absorbed in
S rev the reversible change
T S (J/K)
The Second Law of Thermodynamics: Any spontaneous process is
accompanied by an increase in the entropy of the universe.
The reference point for entropy is provided by The Third Law of
Thermodynamics: There is no disorder in a perfect crystal at 0 K, or S = 0.
All substances have positive entropy values at temperatures above 0 K.

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Sample Problem 1
When ammonia changes from liquid to vapor at
its normal boiling point (239.7K), the heat
absorbed is 29.1 kJ/mol. Calculate the entropy
change of vaporization of ammonia at normal
boiling point.

Solution
When ammonia changes from liquid to vapor at its
normal boiling point (239.7K), the heat absorbed is
29.1 kJ/mol. Calculate the entropy change of
vaporization of ammonia at normal boiling point.

S = q / T = 29.1 103 J / 239.7 K = 121 J K1

i.e., the entropy of 1 mol of ammonia vapour is 121

J K1 greater than the entropy of 1 mol of the liquid.

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Entropy
Entropy increases with the number of
energetically equivalent ways to arrange the
components of a system
The Boltzmann Equation for entropy states:

S = k log W

where k is the Boltzmann constant, and W

represents the number of different ways that the
energy can be distributed over the available
energy levels.

k = Boltzmann Constant = 1.38 x 1023 J/K

W is the number of energetically equivalent ways
a system can exist 7

Entropy and the Second Law of

Thermodynamics
The standard molar entropy (S) of a substance
is the entropy of 1 mol of a substance in its
standard state at a specific temperature.
When comparing the same or similar substances,
the molar entropies of gases are much larger
than those for liquids, and the molar entropies
of liquids are larger than those for solids.

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Relative Standard Entropies: States

The gas state has a larger entropy than the liquid
state at a particular temperature
The liquid state has a larger entropy than the
solid state at a particular temperature

S,
Substance
(J/molK)
H2O (l) 70.0
H2O (g) 188.8
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Standard Molar Entropy of Substances, S

Substances composed of large molecules have
higher molar entropy than substances with
smaller molecules.
Substances whose molecules have complex
structures have more entropy than those with
simpler molecules.
S (J K1 mol1)

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Sample Problem 2
For each of the pair listed, predict which
substance has the higher entropy and explain
your reasoning.
(a) 1 mol of O3(g) or 1 mol of O2(g)
1 mol of O3(g) or 1 mol of O2(g)
(b) 1 mol of SnCl4(g) or 1 mol of SnCl4()
1 mol of SnCl4(g) or 1 mol of SnCl4()
(c) 3 mol of O2(g) or 2 mol of O3(g)
3 mol of O2(g) or 2 mol of O3(g)

Solution
(a) 1 mol of O3(g) has higher entropy than 1 mol of O2(g).
There are 1.5 times as many O atoms in 1 mol of O3(g) than there are in 1 mol of
O2(g) so there are many more possibilities for different arrangements of the
atoms. Ozone has more internal degrees of freedom. Ozone molecules have more
modes of vibration (two stretching vibrations and a bending mode), as well as
three distinct rotational modes. Oxygen molecules have only one stretching
vibrational mode and two rotational modes (rotation about the bond does not
constitute rotation of the molecule). Ozone has more ways of distributing its
energy which corresponds to greater disorderi.e., greater entropy.

(b) 1 mol of SnCl4(g) has more entropy than 1 mol of SnCl4().

Gases have much more entropy per mole than the corresponding liquid. The gas
molecules are free to explore the entire containerliquid molecules have less
volume available and reduced mobility within the bulk.

(c) 3 mol of O2(g) has more entropy than 2 mol of O3(g).

There is the same number of O atomsi.e., 6 mol. 2 mol of the larger molecules is
a more ordered/constrained arrangement of those 6 mol of O atoms than is 3 mol
of O2 molecules. There is more energetically equivalent ways that system can exist
in 3 mol of O2

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Active Learning: Think-Pair-Share

Activity #1

Which substance has the higher entropy in each of the following pairs?

1a. 1 mol of N2(g) at 1 bar or 1b. 1 mol of N2(g) at 10 bar pressure

2a. 1 mol of C2H4(g) or 2b. 1 mol of N2(g)

Solution
1. 1 mol of N2(g) at 1 bar pressure has more entropy
than 1 mol of N2(g) at 10 bar pressure (both at 298
K). Lower pressure means higher volume and
consequently less constrained distribution of
molecules.
2. C2H4(g) has more entropy than N2(g). More
complex molecules have more entropy than less
complex molecules. They have more internal
motions which mean more ways of distributing
energy.

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Entropy and the Second Law of

Thermodynamics
The standard molar entropy (S) of a substanceis the
entropy of 1 mol of a substance in its standard state at a
specific temperature.

Standard Entropy Change of Reaction (rS):

rS = ni S(products) ni S(reactants)

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Sample Problem 3
Calculate the S at 298 K for the following
process.
N2 (g) + 3H2 (g)
2 NH3 (g)

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Solution
N2 (g) + 3H2 (g)
2 NH3 (g)

rS = ni S(products) ni S(reactants)

We predict a decrease in entropy as the reaction converts a total of

4 mol of gas to 2 mol of gas, which is consistent with the calculation.

Active Learning: Think-Pair-Share

Activity #2

Calculate the standard entropy change for the

formation of 1 mol of gaseous ethane (C2H6)
2C(graphite) + 3H 2 (g)
C2 H 6 (g)

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Solution

2C(graphite) + 3H2 (g)

C2 H6 (g)

r S = 1 S o (C2 H 6 ,g) [2 S o (C,graphite) + 3 S o (H 2 , g)]

= 229.2 J K 1 mol1 [2 5.6 J K 1 mol 1 + 3 130.7 J K 1 mol 1 ]
= 174.1 J K 1 mol1

Lecture # 2 on Chapter 17
Spontaneous Change: How Far?

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Lecture Outline
Spontaneous Direction of Change and Equilibrium
Entropy and Second Law of Thermodynamics
Standard Molar Entropy of Substances, S
Entropy Changes and Spontaneity
Gibbs Free Energy and Spontaneity
rG and Ecell for Voltaic Cell Reactions
Dependence of Equilibrium Constants on Temperature
Dependence of Equilibrium Vapour Pressures on
Temperature

Entropy Changes and Spontaneity

A spontaneous process is one that results in an increase of
entropy in the universe.
Suniv = Ssys + Ssurr
The standard entropy change at any specified temperature
can be expressed as:
Suniv = Ssys + Ssurr
The entropy change in the surroundings is proportional to the
amount of heat gained or lost
qsurroundings = qsystem

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Sample Problem 4
Consider the reaction represented as
Si(s) + 2Cl2 (g)
SiCl4 (g)
In a reaction vessel in which all the reactants and products are in
their standard states at 298 K, is this reaction direction indicated
by the chemical equation spontaneous? Answer this question by
calculating Ssys, S surr and S univ

Conceptual Plan:
Calculate Ssys using the formula:
rS = ni S(products) ni S(reactants)

Calculate Ssurr
Suniv = Ssys + Ssurr

Solution
Si(s) + 2Cl2 (g)
SiCl4 (g)

(prior knowledge from section 7.8)

H osys 662.75 103 J mol1

S osurr = = = +2224 J K 1 mol1
T 298K
S o univ = S o sys S o surr = 134.12 J K 1 mol 1 2224 J K 1 mol 1
= 2090 J K 1 mol 1
Since the change in entropy for the universe upon reaction in the
direction indicated by the equation is positive, the reaction is
spontaneous.

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Gibbs Free Energy and Spontaneity

The Gibbs Free Energy, G, is the maximum amount of work
energy that can be released to the surroundings by a system
DGsys = DHsysTDSsys
(-) = (-) - T (+) at high and low T
(+) = (+) - T (-) at high and low T
(-) = (-) - T (-) low T
(+) = (-) - T (-) high T
(+) = (+) - T (+) low T
(-) = (+) - T (+) high T

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Active Learning: Think-Pair-Share

Activity #3

Indicate if the reaction is spontaneous or non-

spontaneous based on the information provided
a) At low temperature
Fe2O3 (s) + 2 Al(s)
2 Fe(s) + Al2 O3 (s) r H o = 851.5kJ mol 1 , r S o = 375.2J K 1 mol1

b) At low temperature
N 2 (g) + 2 O2 (g)
2 NO2 (g) r H = 66.2 kJ mol1 , r S o = 121.6J K 1 mol 1
o

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Solution

Fe2O3 (s) + 2 Al(s)

2 Fe(s) + Al2 O3 (s) r H o = 851.5kJ mol 1 , r S o = 375.2J K 1 mol1

This reaction is spontaneous at low temperature, but NOT

spontaneous at high temperature.

(-) = (-) - T (-) low T

N 2 (g) + 2 O2 (g)
2 NO2 (g) r H o = 66.2 kJ mol1 , r S o = 121.6J K 1 mol 1

This reaction is NOT spontaneous at any temperature

(+) = (+) - T (-) at high and low T

Gibbs Free Energy

The Free Energy Change of Reaction (rG) at any
stage in the reaction can be defined as the following:

rG = ni G (products) ni G (reactants)

However, this equation cannot be used to calculate

rG since the molar free energies of substances are
not known.
rG changes as the amounts of reactants and
products change during chemical reaction.
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Gibbs Free Energy

rG and Spontaneity of Reaction
The second law states that a reaction is spontaneous if
Suniv > 0. A more convenient definition of reaction
spontaneity is as follows:
rG
Suniv
T
If rG < 0, the reaction is spontaneous as written.
If rG = 0, the reaction is at equilibrium.
If rG > 0, the reaction is not spontaneous (but
reaction in the opposite direction is).
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Gibbs Free Energy

Change of free energy of a reaction mixture during reaction.

Copyright 2015 by Nelson Education Limited 30

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Gibbs Free Energy

At any instant during a chemical reaction held at
constant temperature and pressure,
rG = rH TrS
In the particular case of a reaction mixture, in
which all reactants and products are in their
standard states, the free energy change of
reaction is the Standard Free Energy Change of
Reaction (rG)
rG = rH TrS
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Sample Problem 5
Calculate the rG for the following reaction by
calculating the rS and rH

N 2 g + 3 H 2 g
2 NH3 g

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Solution
N 2 g + 3 H 2 g
2 NH3 g
r S = 2 S o (NH 3 ,g) [1 S o (N 2 ,g) + 3 S o (H 2 ,g)]
= 2 192.77 J K 1 mol1 [191.56 J K 1 mol 1 3 130.7J K 1 mol 1 ]
= 198.1 J K 1 mol1

r H = 2 f H o (NH 3 ,g) [ f H o (N 2 ,g) + 3 f H o (H 2 ,g)]

= 2 (45.90 kJ mol1 ) = 91.80 kJ mol1
r G = r H o T r S o
= 91.80 kJ mol1 298 K ( 198.1 J K 1mol1 ) / 1000 J /kJ
= 32.8kJ mol1
Enthalpy Driven Reaction

Active Learning: Think-Pair-Share

Activity #4

Is the following reaction enthalpy driven or entropy driven?

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Solution
C6 H 6 ( ) + 3H 2 (g)
C6 H12 ( ) r H o = 206.7 kJ mol1 , r S o = 316.5J K1 mol 1

rG = rH T rS
= 206.7 kJ mol1 (298 K) (316.5 J K1 mol1) / (1000 J / kJ)
= 112.4 kJ mol1

This reaction is spontaneous at 25C in a reaction mixture with all reagent species in their
standard states. It is enthalpy driventhe negative enthalpy change more than compensates
for the negative entropy change at 25C.

Gibbs Free Energy

The Standard Molar Free Energy Change of
Formation (fG) of a compound is the standard
free energy change when 1 mol of the
compound is formed from its component
elements in their standard states.
By definition, the standard molar free energy
change of formation of an element in its
standard state is zero.
See Appendix D for a list of fG values.
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Gibbs Free Energy

The standard free energy change of a reaction
can be calculated from fG of reactants and
products using the following equation:
rG = ni fG (products) ni fG (reactants)

In any process, the free energy change is the

maximum energy that becomes available to do
useful work. Mathematically,
rG = wmax

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Gibbs Free Energy

Direction of spontaneous reaction in a standard-
state reaction mixture where rG < 0.
K > 1, the reaction is product-favoured

Copyright 2015 by Nelson

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Education Limited

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Gibbs Free Energy

Direction of spontaneous reaction in a standard-
state reaction mixture where rG > 0.
K < 1, the reaction is reactant-favoured

Copyright 2015 by Nelson

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Sample Problem 5

Calculate the rG for the following reaction at

298 K. Is this reaction spontaneous?

3H 2 (g) + CO(g)
CH4 (g) + H2 O(g)

rG = ni fG (products) ni fG (reactants)

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Solution
3H 2 (g) + CO(g)
CH4 (g) + H2 O(g)

rG = ni fG (products) ni fG (reactants)

r G o = 1 f G o (CH 4 ,g) + 1 f G o (H2 O,g) [3 f G o (H2 ,g) + 1 f G o (CO,g)]

= 50.8 kJ mol1 + (228.59 kJ mol1 ) [3 0 kJ mol1 137.168kJ mol1 ]
= 142.2 kJ mol1

This reaction is spontaneous in the forward direction (at 25C, and if all of
the reagents are simultaneously at 1 bar pressure)

Gibbs Free Energy

rH and rS can be assumed temperature

independent over moderate changes of temperature.

When rG = rH T rS, rG = 0, the mixture is at

equilibrium. Using this equation, the temperature at
which the system is at equilibrium can be calculated.

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Sample Problem 6
Use the thermodynamic data of Appendix D to
approximate the temperature at which HgO in a
vessel decomposes sufficiently to be in
equilibrium with 1 bar pressure of O2(g)

2 HgO(s)
2 Hg( ) + O2 (g)

Solution
2 HgO(s)
2 Hg( ) + O2 (g)
r S = 2 S o (Hg,l) 1 S o (O 2 ,g) 2 S o (HgO,s)
= 2 76.02 J K 1 mol1 205.07 J K 1 mol1 2 70.29 J K 1 mol1
= 216.53 J K 1 mol1

r H = 2 f H o (Hg,l) 1 f H o (O 2 ,g) 2 f H o (HgO,s)

= 0 + 0 2 (90.83kJ mol1 ) = +181.66 kJ mol1

r G = r H o T r S o = 0

when

r H o 181.66 1000 J mol 1

T= = = 839.0 K
r S o
216.53 J K 1 mol1

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Active Learning Activity: Think-Pair-

Share Activity #5

The decomposition of liquid nickel carbonyl,

Ni(CO)4 is represented as follows:
Ni(CO)4 ( )
Ni(s) + 4CO(g) r G o at 25oC = 40kJ mol 1

Solution
Ni(CO)4 ( )
Ni(s) + 4CO(g) r G o at 25oC = 40kJ mol 1

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Gibbs Free Energy

Free Energy Change of Reaction in Non-standard
Reaction Mixtures
In practice, very seldom do reaction mixtures have all
species in their standard states. The magnitude of the
difference between the free energies of reaction is as
follows:
rG = rG + RT ln Q
Where R is the universal gas constant, and T is the
temperature in K.
If Q = 1, rG = rG
47

The Relationship Between rG and K

For a specified reaction, rG and K at the same
temperature are mathematically,
0 = rG + RT ln K
rG = RT ln K
This equation allows calculation of an equilibrium
constant at the same temperature as thermochemical
data in tables or obtained from an experiment.
It provides a direct route to determine rG from
experimentally determined equilibrium constants.

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Sample Problem 7
Using the data given in Appendix D, Calculate
the rG and K for the following reaction

C s + CO2 g
2 CO g

Solution

C s + CO2 g
2 CO g
r G o = 2 f G o (CO,g) [1 f G o (C,s) + 1 f G o (CO 2 ,g)]
= 2 ( 137.168 kJ mol 1 ) [0 ( 394.359 kJ mol 1 )]
= 120.023 kJ mol 1

rG o 120.023 103 J mol 1

ln K = =
RT 8.314 J K 1 mol 1 298 K
= 48.44

K = e 48.44 = 9.18 1022

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Active Learning Activity: Think-Pair-

Share Activity #6

The equilibrium constant (K) is 0.14 for the

following reaction. Calculate the rG

N2O4 2NO2
(g) (g)

Solution

rG o = RT ln K = 8.314J K 1 mol 1 298 K ln(0.14)

= 4871 J mol1 = 4.871 kJ mol1

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Lecture # 3 on Chapter 17
Spontaneous Change: How Far?

Lecture Outline
Spontaneous Direction of Change and Equilibrium
Entropy and Second Law of Thermodynamics
Standard Molar Entropy of Substances, S
Entropy Changes and Spontaneity
Gibbs Free Energy and Spontaneity
rG and Ecell for Voltaic Cell Reactions
Dependence of Equilibrium Constants on Temperature
Dependence of Equilibrium Vapour Pressures on
Temperature

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rG and Ecell for Voltaic Cell Reactions

Related Driving Forces of Reaction: rG, K and Ecell
For a spontaneous reaction in a standard-state mixture
(Q = 1), K > 1, Ecell > 0, and rG < 0.

55

Sample Problem 8

Calculate rG, Ecell and K for the following

reaction
2 Fe3+ aq + 2 I aq
2 Fe2+ aq + I2 s

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Solution
2 Fe3+ aq + 2 I aq
2 Fe2+ aq + I2 s

n = 2 here

Ecell = E[Fe3+|Fe2+] E[I2|I] = 0.771 V 0.535 V = 0.236 V

rGo = nFEocell = (2)(96 450 Cmol1 )(0.236V) = 4.55 104 CVmol1 = 45.5kJ mol1

4.55 104 J mol 1

K exp( D rG / RT ) exp 1 1
8.314 J K mol 298 K

9.46 107

Active Learning Activity: Think-Pair-

Share Activity # 7

Calculate the Ecell, rG and K at 25 c for the

following reaction
Zn 2+ aq + Ni s
Zn s + Ni2+ aq

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Solution
Zn 2+ aq + Ni s
Zn s + Ni2+ aq

E = E[Zn2+(aq)| Zn(s)] E[Ni2+(aq)| Ni(s)]

= 0.763 V (0.25 V) = 0.51 V
rG = nF E = 2 96450 C mol1 (0.51 V)
= 98379 CV mol1 = 98.4 kJ mol1

rG o 98.4 103 J mol 1

ln K = =
RT 8.314 J K 1 mol1 298 K
= 39.72

K = e 39.72 = 5.62 1018

Dependence of Equilibrium Constants

on Temperature
For any reaction, rG and K vary as temperature
changes, so we need to relate these values.
The dependence of the equilibrium constant on
temperature is given by the following
relationship
rG = RT ln K = rH TrS

rHo r S o
lnK
RT R
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Dependence of Equilibrium Constants

on Temperature
N2(g) + 3 H2(g) 2 NH3(g)

rHo r S o
lnK
RT R

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Dependence of K on Change of
Temperature
For an exothermic reaction (rHo negative), an increase of
T brings about a smaller value of ln K, and of K.
For an endothermic reaction, increase of T increases K.

rHo r S o
lnK
RT R

Copyright 2015 by Nelson

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Dependence of Equilibrium Constants

on Temperature

The vant Hoff equation can be used to estimate

K at one temperature from an experimentally
measured value at another temperature
rHo 1 1
lnK 1 lnK 2
R T1 T2

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Sample Problem 9

rHo 1 1
lnK 1 lnK 2
R T1 T2
Conceptual Plan:
Calculate the K1
Calculate rH

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Solution
rHo 1 1
lnK1 lnK 2
R T1 T2

Solution

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Solution

Dependence of Equilibrium Vapour

Pressures on Temperature
The dependence of equilibrium vapour pressures of
liquids and solids on temperature is a particular case of
dependence of equilibrium constants on temperature
and corresponding mathematical relationships apply.

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Photochemical Smog and the

Dependence of K on T

Primary pollutants are substances that have

been directly admitted to the atmosphere.

Secondary pollutants are substances formed by

the chemical reactions of primary pollutants.

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Photochemical Smog and the

Dependence of K on T
If a layer of cold air, perhaps polluted, is more dense
than the air above it, it remains trapped near ground
level. This cold layer acts as a reaction vessel, and after
absorbing energy from the sun, pollutants react with
each other.

Copyright 2015 by Nelson

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Photochemical Smog and the

Dependence of K on T

Conditions that are most suited to formation of

photochemical smog:
High concentrations of nitrogen oxides and VOCs.
Thermal inversion.
Relatively still conditions so that the pollutants are
not swept away and diluted by winds.
Long periods of relatively intense sunlight.

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Video: The Science Behind the Smog

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Cumulative Knowledge Testing

on Chapters 16 & 17

Cumulative Knowledge Testing Q#1

From the thermodynamic data provided, (a)
calculate the (Gr) at 298 K, (b) K at 298 K and
(C) K at 1500 C

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Solution
(a) DrG at 298 K
r G o = 2f G o (SO2 ,g) + 1 f G o (O2 ,g) 2f G o (SO3 ,g)
= 2( 300.13kJ mol1 ) 0 kJ mol1 2( 371.04 kJ mol1 )
= 141.82 kJ mol1
(b) K at 298 K

rG o 141.82 103 J mol 1

ln K = =
RT 8.314 J K 1 mol 1 298 K
= 57.24

K = e 57.24 = 1.38 1025

Solution
c) K at 1500 C

rG o 141.82 103 J mol 1

ln K = =
RT 8.314 J K 1 mol 1 1773 K
= 9.62

K = e 9.62 = 6.64 105

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Cumulative Knowledge Testing Q#2

Consider the half reactions given below to answer the following
questions

E[Ni2+(aq)|Ni(s)] = 0.25 V
E[Cd2+(aq)|Cd(s)] = 0.403 V
a) Which half reaction is taking place at the cathode?
b) What is the Ecell ?
c) If a salt bridge containing NaNO3 connects the two half cells,
which way the NO-3ions move?
d) Calculate the equilibrium constant for the cell reaction at 298 K.
e) If the concentration Cd+2(aq) ions is reduced to 0.010 M, keeping
the the [Ni+2] 1 M, what is the Ecell

Solution
(a) Since Ni2+(aq)|Ni(s) has the higher reduction
potential, the Ni(s) electrode is the cathode.

(b) Ecell = E[Ni2+(aq)|Ni(s)] E[Cd2+(aq)|Cd(s)]

= 0.25 V (0.403 V) = +0.15 V

(c) The NO3(aq) ions (anions) move toward the anode

compartment.

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Solution
(d)
DG = RTlnK = nFEcell
2 2
ln K = E o cell = (+ 0.15 V)
0.0257 V 0.0257 V
= 11.7
and
K = 1.2 105

Solution
(e) RT 0.0257V
Ecell E o cell ln Q E o cell ln Q at 25o C
nF n

0.0257 V 0.0257 V [Cd2 ]

Ecell = E o cell ln Q = + 0.15 V ln 2
n 2 [Ni ]
0.0257 V 0.010
= + 0.15 V ln = + 0.21V
2 1.0

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