TOPICS IN PHYSICAL CHEMISTRY

Chem 233

Part II
ELECTROCHEMISTRY
Theo van de Ven
theo.vandeven@mcgill.ca

Office hours: Tuesday 2:00– 4;00 pm

Room 108 P&P
1
 Definition of electrochemistry

The branch of physical chemistry that deals with the

relations between electrical and chemical phenomena

Applications of electrochemistry
• Batteries • Electrolithography
• Fuel cells • Corrosion, corrosion inhibition
• Solar cells • Scaling, chronoamperometry
• Electrolysis • Brain chemistry
• Electroplating • Medicine
• pH measurements • Electrosynthesis
• Characterization • Mineral extraction
• etc. 2
 Usage of electrochemistry

Three major uses

• Converting chemical energy into electrical energy

• Storage of electrical energy in the form of chemical energy
• Making use of electrically produced chemical energy
• Use of electrical energy in making chemicals and materials
• Used as a tool for characterizing and analyzing chemicals and materials
• Used to separate materials
• Used as a tool for understanding natural electrochemical processes

3
 Pseudo-history of electrochemistry
The Baghdad “battery” 600-300 BC

4
 Pseudo-history of electrochemistry
The Baghdad “battery” 600-300 BC Iron rod

Copper
cylinder

Can indeed produce a voltage

of 0.8 V, when filled with an acid

5
 Pseudo-history of electrochemistry
The Baghdad “battery” 600-300 BC

Much more likely explanation:

it was a scroll holder

6
A bit of history

Giants in electrochemistry

Alessandro Volta
Inventor of the battery in 1800
Disproves Galvani’s
"nerveo-electrical substance"

Sir Humphry Davy

Systematic studies of Volta’s battery
First scientist to establish link between
electricity and chemical reactions and
realizing that a chemical bond is
electrical in origin
7
Scientific Researches! New Discoveries in Pneumaticks! An Experimental Lecture on
the Powers of Air, 1802. James Gillray’s satirical etching depicts Davy and colleagues 8
experimenting with nitrous oxide.
 The speech and demonstration that made Davy famous. 9
engraving from Rudolph Ackermann’s Microcosm of London (1808–1810)
Davy using a voltaic battery to experiment with the decomposition of alkalis.
Bettmann/Corbis

10
Michael Faraday
Davy’s student and successor
First electric motor (in 1821)
First dynamo (in 1831)
First laws of electrochemistry

11
Michael Faraday in his laboratory at the Royal Institution.
From a painting by Harriet Moore. Science History Institute

12
Michael Faraday’s concern about contemporary environmental problems
caricatured. From Punch, July 21, 1855. Science History Institute 13
 John Frederic Daniell
(1790-1845)

Self-taught chemist
Most important contribution
development of one of the earliest
batteries, the Daniell Cell (1831)
It supplies electricity for a longer
time than the previous Voltaic Cell 14
 References

• P.H. Rieger, Electrochemistry, Chapman & Hall

• Fundamentals of electrochemistry, V. S. Bagotsky, Wiley

• Principles of electrochemistry, D. A. MacInnes, Dover

• The elements of physical chemistry, P.W. Atkins, Oxford

University Press

15
 Topics
• Electrolyte solutions
• Electrode potentials
• The electrified interface
• Activity coefficients
• Electrolyte conductance
• Voltammetry
• Electrolysis

Course evaluation:

• class tests, problem assignments

• questions at final exam
16
 Lecture 1

Electrolyte solutions

17
Main components in electrochemical experiment

An electrochemical cell consists of

• an electrolyte solution, or two (separated by a liquid junction)

• two or more electrodes
• paraphernalia
• cables, connections
• electrical circuits
• detectors (voltmeters, amperometers, etc.)
• software

The first few lectures will be on electrolyte solutions and electrodes

18
 Electrolytes
Substances that give ions when dissolved in water are called
electrolytes. They can be divided into acids, bases and salts
because they all give ions when dissolved in water.

19
 Electrolytes
Substances that give ions when dissolved in water are called
electrolytes. They can be divided into acids, bases and salts
because they all give ions when dissolved in water.

An acid donates a proton to the solution (more precise definition later)

A base donates an hydroxyl ion to the solution ( ” )
A salt is a compound formed in a reaction between an acid and a base
Example: HCl ® H + + Cl- NaOH ® Na + + OH - NaOH + HCl ® NaCl + H 2O
acid base salt

20
 Electrolytes
Substances that give ions when dissolved in water are called
electrolytes. They can be divided into acids, bases and salts
because they all give ions when dissolved in water.

An acid donates a proton to the solution (more precise definition later)

A base donates an hydroxyl ion to the solution ( )
”
A salt is a compound formed in a reaction between an acid and a base

Example: HCl ® H + + Cl- NaOH ® Na + + OH - NaOH + HCl ® NaCl + H 2O

acid base salt

Positive ions are called cations and negative ions are called anions

An electrolyte solution is a solution that contains ions

These solutions conduct electricity due to the mobility of the positive

and negative ions. 21
Electrolytes can be divided into strong electrolytes and weak electrolytes

Strong electrolytes completely ionize when dissolved, and no

neutral molecules are formed in solution. E.g.:
+ -
NaCl(s) ® Na (aq) + Cl(aq)
To this class also belong strong acids and strong bases
e.g. HCl and NaOH

22
Electrolytes can be divided into strong electrolytes and weak electrolytes

Strong electrolytes completely ionize when dissolved, and no

neutral molecules are formed in solution. E.g.:
+ -
NaCl(s) ® Na (aq) + Cl(aq)
To this class also belong strong acids and strong bases
e.g. HCl and NaOH

Weak electrolytes dissolve in water only to a limited extent, e.g. sparsely

soluble salts, as well as weak acids and weak bases

Example of weak acid:

+
Example of weak base: NH3 + H2O Ä NH4(aq) + OH -
2+ 2-
Example of a sparingly soluble salt: CaCO3(s) Ä Ca (aq) + CO3(aq)
23
 Equilibrium constants
- +
Example HCOOH (aq) Ä HCOO(aq) + H (aq)

d [ HCOOH ]
= k1 é HCOO - ù é H + ù - k 2 [ HCOOH ]
dt ë ûë û

24
 Equilibrium constants
- +
Example HCOOH (aq) Ä HCOO(aq) + H (aq)

d [ HCOOH ]
= k1 é HCOO - ù é H + ù - k 2 [ HCOOH ]
dt ë ûë û
Formation of HCOOH Dissociation of HCOOH

25
 Equilibrium constants
- +
Example HCOOH (aq) Ä HCOO(aq) + H (aq)

d [ HCOOH ]
= k1 é HCOO - ù é H + ù - k 2 [ HCOOH ]
dt ë ûë û
Formation of HCOOH Dissociation of HCOOH

As t → ∞ k1 é HCOO- ù é H + ù - k 2 [ HCOOH ] = 0
ë ûë û
é HCOO- ù é H + ù
ë û ë û = k2 = K
[ HCOOH] k1
eq

Equilibrium constant
When relating Keq to thermodynamic quantities
all concentrations must be converted to activities 26
 Activities and activity coefficients

o
For an ideal gas a = P/P
o o
For an ideal solution a = C/C where C = 1M (mol/L)

For pure liquids and solids a =1

o
For non-ideal solutions a = γ C/C

γ is activity coefficient

27
 All weak acids, weak bases and weak salts
have an equilibrium constant associated with them

For strong acids, strong bases and strong salts

the equilibrium constant is extremely large

Water is a very weak electrolyte.

Autoionization of pure water:
H 2O Ä H + + OH -
K w = é H + ù éOH - ù = 1.0 ×10-14
More precise:
ë ûë û

a H+ a OH- -14
pH = - log a H+
Kw = = a H + a OH - = 1.0 ×10
a H 2O
pH of pure water is 7
28
pH measurements
• litmus paper • pH meter (electrochemical measurement)

29
 of weak (sparingly soluble) salts

table 30
31
32
 Equilibria of calcium carbonate
with water and air
2+ 2-
CaCO3(s) Ä Ca (aq) + CO3(aq) K1 = 4.28 ×10-9 (calcite)

K1 = 6.54 ×10-9 (aragonite)

K1 = 1.23 ×10-8 (vaterite)
2- - -
CO3(aq) + H 2O É HCO3(aq) + OH(aq) K 2 = 2.19 ×10-4
- -
HCO3(aq) + H 2O É H 2CO3(aq) + OH(aq) K3 = 2.07 ×10-8

H 2CO3(aq) É CO2(g) + H 2O K 4 = 27.2

33
 Hairy nanocelluloses for
bioinspired mineralization,
A. Sheikhi, A. Kakkar and
T.G.M. van de Ven,
Crystal Growth & Design
16(8), 4627-4634 (2016)

calcite vaterite

aragonite
https://www.researchgate.net/post/How_does_aragonitic_
limescale_form_inside_the_boiler_system_of_vending_machines 34
 Effect of salt on pH of CaCO3 suspended in H 2 O

NaCl affects
activity coefficients
of other ions

pH in
seawater
CaCO3 Ä Ca 2+ + CO32-

CO32- + H 2O É HCO3- + OH -
[Ca 2+] in seawater

Adding Ca 2+causes pH to drop

35
 Effect of CO2 on seawater pH
2+ 2-
CaCO3(s) Ä Ca (aq) + CO3(aq)
[Ca2+ ] ≈ constant,
not determined buffered
by CaCO
3
H 2O Ä H + + OH -
2- - -
Little affected CO3(aq) + H 2O É HCO3(aq) + OH(aq)

- -
HCO3(aq) + H 2O É H 2CO3(aq) + OH(aq)

H 2CO3(aq) É CO2(g) + H 2O
Increasing [CO 2 ] reduces pH
36
Dissolution of CO 2 in pure water also causes pH to drop

CO 2(g) + H 2O Ä H 2CO3

H 2CO3 Ä H + + HCO3-
Hence pH ↓

Concentration of CO32- negligible below pH 7

Dissolution of CO will affect all weak acid or base solutions

2

37
 The Brønsted - Lowry theory
of acids and bases

A Brønsted acid is a proton donor

A Brønsted base is a proton acceptor

Examples Johannes Nicolaus Brønsted

(1879 –1947)
HCl is an acid, because it can give a proton to
water: H + + H 2O ® H3O+
hydronium ion
NH is a base, because it can accept a proton
3
NH3 + H + ® NH +4
SO24- is a base SO24- + H + ® HSO-4

Thomas Martin Lowry

38
(1874 – 1936)
 Consider the following equilibrium of a weak acid
+ -
HA(aq) + H2O Ä H3O(aq) + A(aq)
In the forward reaction H 2O accepts a proton and thus is a Brønsted base

HA donates a proton and is a Brønsted acid

+
In the reverse reaction H3O donates a proton and is a Brønsted acid

A- accepts a proton and is a Brønsted base

+ -
HA(aq) + H2O Ä H3O(aq) + A(aq)
-
H3O+ is conjugate acid of base H 2O and A is the conjugate base of acid HA

39
 The general form of the Brønsted proton
transfer equilibrium in water

acid1 + base2 Ä acid 2 + base1

(acid , base ) one conjugated acid-base pair, and

1 1
(acid2 , base2 ) another conjugated acid-base pair

+ -
Another example H2O (l ) + NH3( aq) Ä NH4( aq) + OH ( aq)

acid1 + base2 Ä acid 2 + base1

Autoprotolysis H2O (l ) + H2O (l ) Ä H3O+( aq) + OH- ( aq)

of water
acid1 + base2 Ä acid 2 + base1
40
 Acidity and basicity constants

é HCOO- ù é H + ù
-
HCOOH(aq) Ä HCOO(aq) +
+ H(aq) Ka = ë ûë û
[ HCOOH]
é NH +4 ù éOH - ù
+
H2O (l ) + NH3( aq) Ä NH4( + OH - Kb = ë ûë û
aq) ( aq)
[ NH3 ]

Since each acid and base has an associated conjugated base and acid

acid1 + base2 Ä acid 2 + base1

we can assign both a K a and K b value to each acid or base

Ka × K b = K w
41
42
43
 Colligative properties of electrolyte solutions

Colligative properties of electrolyte solutions are properties that depend

upon the concentration of ions, but not upon the identity of the solute or
on the type of ions.

Colligative properties include

• osmotic pressure
• vapor pressure lowering
• boiling point elevation
• freezing point depression
The first two are relevant to electrochemistry

44
 Osmotic pressure
Compare a box filled with gas molecules
with a box filled with an electrolyte solution

Gas molecules move around in the box
Gas molecules exert a pressure on the
wall and everywhere within the gas
Pressure P given by the ideal gas law
PV = NRT or P = nRT
number of moles number per unit volume
Ions move around in the box
Ions exert a pressure on the wall
and everywhere within the solvent
Pressure π given by van‘t Hoff law
p = nRT
45
Jacobus Henricus van 't Hoff
(1852 – 1911)
Nobel Prize 1901

46
 Criticism of van ‘t Hoff by Kolbe

I (i.e. Kolbe) have recently published an article in the Journal

für praktische Chemie (14, 288 ff.) giving as one of the reasons
for the contemporary decline of chemical research in Germany
the lack of well-rounded and thorough chemical education. Many
of our chemistry professors labor with this problem to the great
disadvantage of our science. As a consequence of this, there is
an overgrowth of the weed of the seemingly learned and
ingenious but in reality trivial and stupefying natural philosophy.
This natural philosophy, which had been put aside by exact
science, is at present being dragged out by pseudoscientists
from the junk-room of science which harbors such failings of the
human mind, and is dressed up in modern fashion, all dolled up,
like a whore whom one tries to smuggle into good society where
she does not belong.
47
Whoever considers this apprehension to be exaggerated
should read, if he can stomach it, the recently published
paper," The arrangement of atoms in space", by van 't Hoff
and Herrmann, which teems with fantastic trifles. I would
ignore this paper as so many others if it were not for a
renowned chemist who protected this nonsense and
recommended it warmly as meritorious accomplishment.
A. J. H. van 't Hoff who is employed at the Veterinary
School in Utrecht appears to find exact chemical research not
to his taste. He deems it more convenient to mount Pegasus
(evidently loaned from the Veterinary School) and to proclaim
in his "La chimie dans l'espace" how, to him, on his chemical
Parnassus which he ascended in his daring flight, the atoms
appeared to be arranged in the Universe.
48
49
 Measurement of osmotic pressure
Acceleration
Osmotic pressure is measured
with an osmometer π=gdh
Density
p = nRT

Measuring π
yields n, semi-permeable
the number of membrane
particles or
equivalently
the number of ions electrolyte
per unit volume solution

50
What we have learned so far

• A bit of the history of electrochemistry

• The components of an electrochemical cell
• Some properties of electrolyte solutions
• Acids, bases and salts
• Strong and weak electrolytes
• Brønsted acids and bases
• Conjugated acid-base pairs
• Equilibrium constants
• Solubility constant (solubility products)
• Acidity and basicity constants
• Effect od CO2 on pH of water
• Colligative properties
• Osmotic pressure

51
Thermodynamics of electrolyte solutions

For closed systems: G = U + PV – TS

dG = VdP - SdT

For open systems: dG = VdP - SdT + å µidn i

i =1,2

æ ¶G ö G = G o + RT ln a
µi = ç ÷ µ = µo + RT ln a
è ¶n i øp,T,n j¹i

Chemical potential

52
 G = G o + RT ln a
Example
µ = µo + RT ln a
2+ 2-
CaCO3(s) Ä Ca (aq) + CO3(aq)

µCaCO3(s) = µoCaCO3(s)
o
o
µCa 2+ = µCa 2+ + RT ln a µCO2- = µCO 2- + RT ln a CO2-
(aq) (aq) Ca 2+ (aq) 3(aq) 3(aq) 3(aq)

Change in Gibbs free DG r = µCa 2+ + µCO2- - µ CaCO3(s)

(aq) 3(aq)
energy due to reaction
a Ca 2+ a CO2-
= DG or + RT ln
(aq) 3(aq)

a CaCO3(s)
At equilibrium
In general: DG r = DGor + RT ln K eq
DG o = -RT ln K eq
53
Josiah Willard Gibbs
(1839 – 1903)

54
 Vapor pressure
The vapor pressure of a liquid is the equilibrium pressure of a vapor above
its liquid, i.e. the pressure of the vapor resulting from evaporation of a
liquid above a sample of the liquid in a closed container.

Water vapor pressure

55
Vapor pressure as a function of NaCl concentration

P
Po

Y. A. Perez Sirkin,et al., J. Chem. Theory Comput. 12, 2942 (2016)

56
pure liquid electrolyte solution

The presence of electrolytes alters

the vapor pressure
57
Chemical potential and vapor pressure

PV = NRT Ideal gas law

P
G = G o + RT ln
Po
P
Per mole: µ = µ o + RT ln
Po

58
EXAMPLE

Which would have the lowest vapor pressure at 25 oC?

a) 0.1 M solution of NaCl
b) 0.1 M solution of C 6 H12 O 6 (glucose)
c) 0.1 M solution of Al(NO3 ) 3

59
EXAMPLE

Which would have the lowest vapor pressure at 25 oC?

a) 0.1 M solution of NaCl
b) 0.1 M solution of C H O (glucose)
6 12 6
c) 0.1 M solution of Al(NO3 ) 3

Answer
The correct answer is c.
All of the solutions have the same concentration,
but when NaCl dissolves, it splits into 2 ions.
Glucose is a non-electrolyte and does not break apart.
When Al(NO 3) 3 dissolves, it produces 4 ions in solution
(1 Al 3+ and 3 NO-3 ), and will have the greatest impact on the
vapor pressure, a colligative property
60
 Molarity, molality and normality
Molarity (M) is defined as the number of moles of solute per liter of solution.
molarity = moles of solute/liters of solution

Molality (m) is the number of moles of solute per kilogram of solvent.

molality = moles of solute/kilograms of solvent

Normality (N) is the number of mole equivalents per liter of solution:

normality = number of mole equivalents/1 L of solution

When water is the solvent and the concentration of the solution is low, the
difference between Molarity and Molality can be negligible (d = 1.00 g/mL).
When d is significantly different than 1 the difference becomes more evident.

Normality specifically used for acids and bases. N = n·M, n being the number
of H + or OH- . E.g. 1 M H2 SO4 = 2 N H2 SO4
61
 Medical applications
Medical electrolyte solutions must be tailored to restore and maintain
a proper homeostatic environment.

Homeostasis is the state of steady internal conditions maintained by

living things.

To assist in the treatment and recovery process, doctors often introduce

electrolyte solutions into the body. The solutions must be of proper osmolality
and concentrations, otherwise irreversible damage can be caused.

Plasma osmolality is a measure of the electrolyte -water balance in blood.

Osmolality: The molality of an ideal solution that would exert the same
osmotic pressure as the solution being considered.
hypotonic: Having a lower osmotic pressure than that of another solution.
hypertonic: Having a greater osmotic pressure than another solution.

62
 Physiologic(al) salt solution
A physiologic salt solution, also called a saline solution is a NaCl
solution of 0.9 g/100 mL (0.154 M)

A saline solution is isotonic with blood plasma (i.e. it has the same
osmotic pressure)

Its main use is to rehydrate and carry ions needed for cellular activity
into the body, often used intravenously.

Hypertonic solutions cause cells to shrink and shrivel

Hypotonic cause cells to expand and burst

63
64
 Effect of temperature on acid-base equilibria

We have seen that in general for any chemical reaction at equilibrium

DG o = -RT ln K eq
and DGo = DHo - TDSo H = U + PV H is enthalpy

DG o DHo DSo
hence at temperature T ln K = - =- +
RT RT R
o o o
DG DH DS
and at temperature T’ ln K’ = - =- +
RT’ RT’ R

hence K’ DHo æ 1 1 ö
ln = ç - ÷
K R è T T ’ø

equation due to van ‘t Hoff 65

 Le Chatelier’s principle

o ΔHo > 0 corresponds to an endothermic reaction

K’ DH æ 1 1 ö i.e, a reaction requiring absorption of heat
ln = ç - ÷
K R è T T ’ø
ΔHo < 0 corresponds to an exothermic reaction
i.e, a reaction in which heat is released

66
 Le Chatelier’s principle

o ΔHo > 0 corresponds to an endothermic reaction

K’ DH æ 1 1 ö i.e, a reaction requiring absorption of heat
ln = ç - ÷
K R è T T ’ø
ΔHo < 0 corresponds to an exothermic reaction
i.e, a reaction in which heat is released

If T’ is larger than T and ΔH is positive, than K’ > K, hence for an

endothermic reaction K increases with increasing temperature
Similarly for an exothermic reaction K decreases with an increase in T

67
 Le Chatelier’s principle

o ΔHo > 0 corresponds to an endothermic reaction

K’ DH æ 1 1 ö i.e, a reaction requiring absorption of heat
ln = ç - ÷
K R è T T ’ø
ΔHo < 0 corresponds to an exothermic reaction
i.e, a reaction in which heat is released

If T’ is larger than T and ΔH is positive, than K’ > K, hence for an

endothermic reaction K increases with increasing temperature
Similarly for an exothermic reaction K decreases with an increase in T
A reduction in temperature favors an exothermic reaction because the
heat released tends to oppose the lowering of temperature.

Hence the temperature dependence is in agreement with Le Chatelier’s

principle:

When a system at equilibrium is disturbed, the system

adjusts itself as to minimize the effect of the disturbance
68
 Effect of pressure on chemical equilibria
DG o = -RT ln K eq
Since all standard states refer to a standard pressure of 1 atm (1 bar),
ΔGo and hence also the equilibrium constant is independent of pressure

69
 Effect of pressure on chemical equilibria
DG o = -RT ln K eq
Since all standard states refer to a standard pressure of 1 atm (1 bar),
ΔGo and hence also the equilibrium constant is independent of pressure

Although the value of K does not depend on pressure, partial pressures,

which may enter the expression for K, could depend on pressure

70
 Effect of pressure on chemical equilibria
DG o = -RT ln K eq
Since all standard states refer to a standard pressure of 1 atm (1 bar),
ΔGo and hence also the equilibrium constant is independent of pressure

Although the value of K does not depend on pressure, partial pressures,

which may enter the expression for K, could depend on pressure

Consider the following reaction H2(g) + I2(s) Ä 2HI(g)

a 2HI PHI
2
Po PH 2 PHI
,
K= = 2 partial pressures
Po Po
a H 2 Po PH 2
cannot stay constant for constant K,
if e.g. pressure is increased
increase decrease
71
 Shift of equilibrium composition with pressure

H2(g) + I2(s) Ä 2HI(g)

For the equilibrium constant to remain constant, the equilibrium
composition must change with pressure.

The change in composition can be predicted by Le Chatelier’s principle:

When a system at equilibrium is compressed, the composition of the gas

adjusts itself so as to reduce the number of molecules in the gas phase

Thus for the reaction considered, the reaction shifts to the left when the
pressure is increased (without affecting K).

72
Industrial relevance of Le Chatelier’s principle
Industrial production of ammonia

The reaction N2(g) + 3H2(g) Ä 2NH3(g) is exothermic.

Hence according to Le Chatelier’s principle, the equilibrium constant

decreases as the temperature is increased, (at 200 oC, K < 1).
The reaction is slow and the reaction is not economically viable.

However Le Chatelier’s principle also offers a solution: Increase pressure

At higher pressures, according to Le Chatelier, the number of molecules in

the gas phase will be reduced, i.e. the reaction shifts to the right

This is the basis of the Haber process for the industrial production of NH3 ,
which allowed the large scale production of fertilizers and a phenomenal
growth in agricultural production 73
Henry Louis Le Chatelier Fritz Haber

(1850 – 1936) (1868-1934)

74
 Take home messages
• Acids can be defined as proton donors, bases as proton acceptors
(Brønsted - Lowry theory)
• Equilibrium constants can be obtained from standard Gibbs free
energies ( DG o = -RT ln K eq ) which, as we will see later, can be obtained
from electrochemical cell potentials
• In equilibrium constants concentrations must be expressed as activities
• Gibbs free energies have an enthalpic and an entropic contribution
(DG = DH - TDS )
• Equilibrium constants depend on temperature, but not on pressure
• Changes in equilibrium composition, due to temperature or pressure,
can be rationalized by Le Chatelier’s Principle
• As a good approximation, osmotic pressures of electrolyte solutions
resemble pressures in a gas phase (van ‘t Hoff law)
• Osmotic pressures and lowering of vapor pressure are colligative
properties of electrolyte solutions

75