CHM520 CompleteBranchLectureNotes

Physical Chemistry II – Thermodynamics Prepared by Chan Chin Han
Physical Chemistry II (CHM 520)
Lecture (3 hrs/week); Practical (3 hrs/week)
Course Outcomes
Upon completion of this course, students should be able to:
1. Assess concepts for thermodynamics, solutions of electrolytes,

electrochemical cells and radiochemistry, to solve qualitative &
quantitative problems algebraically and numerically.
2. Conduct scientific investigation in areas on thermodynamics,

solutions of electrolytes, electrochemical cells and
radiochemistry.
3. Communicate in writing the scientific investigations.
Course Description
This course will interactively engage students cognitively and
scientifically in areas of thermodynamics, electrochemistry and
radiochemistry. Students will define concepts, make predictions as to
the possible outcome of an event and perform investigations via
laboratory exercises. The designated lecture session is used to
discuss results of investigations leading to its relation to the existing
laws, principles or theories. Lecture sessions employ a mixture of
lectures and problem based learning. The outcomes shall be
assessed through a variety of tools which include the traditional paper
examination, informal interviews and classroom engagement.
1
Contents
1.0 Thermodynamics.
1.1 Temperature and the zeroth law of thermodynamics.
1.2 First law of thermodynamics.
1.3 Second law of thermodynamics.
1.4 Third law of thermodynamics.
Lab 1: Heat-capacity ratios for gases.

Lab 2: Determination of change of standard Gibbs free energy.
2.0 Solutions of electrolytes.

2.1 Properties of electrolytes.
2.2 Electrolytic Deposition.
2.3 The Process of conduction.
Lab 3: Faraday’s laws.

Lab 4: Determination of molar conductivity at infinite dilution of strong
electrolyte.
Lab 5: Degree of dissociation and equilibrium constant for weak electrolyte.
3.0 Electrochemical cells.

3.1 Components of a cell.
3.2 Conventional representation of a cell.
3.3 Potentials of cells and electrodes.
3.4 Thermodynamics of cells.
3.5 Types of electrodes and general form of Nernst equation for an electrode.
3.6 Types of galvanic cells and general form of Nernst equation for a galvanic
cell.
3.7 Applications of Galvanic cell potentials.
Lab 6: Electrochemistry and thermodynamics.

Lab 7: Determine the equilibrium constant for a galvanic cell.
4.0 Radiochemistry.
4.1 Types of radioactive decay.
4.2 Balancing nuclear equations.
4.3 Radioactive decay rates.
4.4 Nuclear stablility.
4.5 Nuclear reactions.
4.6 Radiation detection.
4.7 Applications of radioactive nuclides.
2
The lecture notes of Thermodynamics of CHM 520 are adopted from Atkins
P, Paula JD. Atkins’ Physical Chemistry, 8th Ed., Oxford University Press,
2006
The First Law
Basic Concepts
• Thermodynamics are the study of the transformations of energy.
• The universe is divided into:

1. the system –
2. its surroundings –
They are boundary between them.
Surroundings
Matter
System
Energy
3
Surroundings
Matter
System
Energy
Surroundings
Matter
System
Energy
4
5
Work, heat and energy
Thermodynamics is concerned with energy changes that accompany

a process.
A process that does work is one that could be used to bring about a
change. (e.g. change in the height of a weight somewhere in the
surroundings)
Energy of a system is its capacity to do work. (e.g. by winding a

spring, its capacity to do work is increase and thus the energy of the
system is increased.)
When the energy of a system changes as a result of a temperature

difference between it and its surroundings we say that energy has
been transferred as heat.
Exothermic –
Endothermic –
A wall is diathermic if a change of state is observed when two objects

at different temperatures are brought into contact. (e.g. a metal
container)
Low High
temperature temperature
heat
6
Endothermic process Exothermic process
heat heat
In a diathermic container, In a diathermic container,

energy enters as heat for the energy leaves as heat to the
surroundings, and the surroundings, and the
system remains at the same system remains at the same
temperature - isothermal temperature - isothermal
A wall is adiabatic if no change occurs even though the two objects

have different temperatures. (e.g. Dewar vessel)
Endothermic process Exothermic process
In an adiabatic system, the In an adiabatic system, the

temperature falls. temperature rises.
7
The First Law
Internal energy, U –
ΔU –
The internal energy is a state function in the sense that its value
depends only on the current state of the system and is independent
of how that state has been prepared.
Unit for U, w, q are joule (J).
In a closed system, the change in internal energy is equal to the

energy that passes through its boundary as heat or work.
Note: the internal energy of an isolated system is constant.
Work and Heat
8
Expansion work – the work arising from a change in volume.
e.g. the work required to move an object a distance dz against an

opposing force F is
External pressure, Pex
Area, A
Distance
move, dz
Pressure, P
9
Reversible expansion:
A reversible change in thermodynamics is a change that can be
reversed by an infinitesimal modification of a variable.
To achieve reversible expansion we set pex equal to p at each stage

of the expansion. In practice, this equalization could be achieved by
gradually removing weights from the piston so that the downward
force due to the weights always matched the changing upward force
due to the pressure of the gas.
Isothermal reversible expansion: (of a perfect gas)
10
when Vf > Vi (expansion), w < 0. So, the system has done work on
the surroundings and the internal energy of the system has decrease
as a result of the work it has done.
Calculation
Calculate the work done when 50 g of iron reacts with hydrochloric
acid in: (a) a closed vessel of fixed volume; (b) an opened beaker at
25 oC.
11
Heat and Enthalpy
At constant volume, no additional work,
For measurable change,
Heat capacity
The internal energy of a substance increases when its temperature is

raised. The increase depends on the conditions under which the
heating takes place and for the present we suppose that the sample
is confined to a constant volume.
For example, the sample may be a gas in a container of fixed volume.

If the internal energy is plotted against temperature, then a curve like
that in Fig. 10 may be obtained. The slope of the tangent to the curve
at any temperature is called the heat capacity of the system at that
temperature.
Heat capacity at constant volume, Cv (J K-1)

 ∂U 
Cv =  
 ∂T V
Heat capacities are extensive properties:
e.g.: 100 g of water has 100 times the heat capacity of 1 g of water
(and therefore requires 100 times the energy as heat to bring about
the same rise in temperature).
Molar heat capacity at constant volume, Cv,m (J K-1 mol-1) – the heat
capacity per mole of material and is an intensive property (all molar
quantities are intensive).
CV,m = CV/n
12
−1 −1
e.g.: CV,m for polyatomic gases are close to 25 J K mol .
Specific heat capacity (J K-1 g-1) - heat capacity per unit mass.
(Usually per gram of material).
CV,s = CV/m
−1 −1
e.g.: CV,s of water at room temperature is close to 4 J K g .
In general, heat capacities depend on the temperature and decrease

at low temperatures. However, over small ranges of temperature at
and above room temperature, the variation is quite small and for
approximate calculations heat capacities can be treated as almost
independent of temperature.
If the heat capacity is independent of temperature over the range of

temperatures of interest, then a measurable change of temperature
ΔT brings about a measurable increase in internal energy ΔU
*Fig. 10 The internal energy of a system increases as the temperature is raised;

this graph shows its variation as the system is heated at constant volume. The
slope of the tangent to the curve at any temperature is the heat capacity at
constant volume at that temperature. Note that, for the system illustrated, the
heat capacity is greater at B than at A.
13
Enthalpy
The change in internal energy is not equal to the heat supplied when
the system is free to change its volume. Under these circumstances
some of the energy supplied as heat to the system is returned to the
surroundings as expansion work. So, dU < dq.
Fig. 12 When a system is subjected to constant pressure and is free

to change its volume, some of the energy supplied as heat may
escape back into the surroundings as work.
In this case, the heat supplied is equal to the change in another

thermodynamic property of the system, the enthalpy (H).
A change in enthalpy is equal to the heat supplied at constant

pressure to a system. (The system does no additional work)
For a measurable change,
If a process involves only solids or liquids, the values of ΔH and ΔU

are almost identical. Physically, such processes are accompanied by
a very small change in volume; the system does negligible work on
14
the surroundings when the process occurs, so the energy supplied as

heat stays entirely within the system.
The enthalpy of a perfect gas:
This relation implies that the change of enthalpy in a reaction that

produces or consumes gas is
Δng is the change in the amount of gas molecules in the reaction.
e.g. 2H2 (g) + O2 (g) → 2H2O (l),
15
The variation of enthalpy with temperature
The enthalpy of a substance increases as its temperature is raised.

The relation between the increase in enthalpy and the increase in
temperature depends on the conditions (for example, constant
pressure or constant volume).
The most important condition is constant pressure, and the slope of

the tangent to a plot of enthalpy against temperature at constant
pressure is called the heat capacity at constant pressure (Cp) at a
given temperature.
Heat capacity at constant pressure, Cp,
 ∂H 
Cp =  
 ∂T  P
Molar heat capacity at constant pressure, Cp,m (J K-1 mol-1) – the heat
capacity per mole of material.
Specific heat capacity (J K-1 g-1) - heat capacity per unit mass.
(Usually per gram of material)
16
The heat capacity at constant pressure is used to relate the change in

enthalpy to a change in temperature. For infinitesimal changes of
temperature,
 ∂H 
Cp =  
 ∂T  P
If the heat capacity is independent of temperature over the range of

temperatures of interest, then a measurable change of temperature
ΔT brings about a measurable increase in ΔH
The variation of heat capacity with temperature can sometimes be

ignored if the temperature range is small; this approximation is highly
accurate for a monatomic perfect gas (for instance, one of the noble
gases at low pressure). However, when it is necessary to take the
variation into account, a convenient approximate empirical expression
is
c
Cp, m = a + bT +
T2
17
The empirical parameters a, b, and c are independent of temperature.
18
Example:
Evaluating an increase in enthalpy with temperature
What is the change in molar enthalpy of N2 when it is heated from

25°C to 100°C? Use the heat capacity information in Table 2.2.
Solution:
19
Most systems expand when heated at constant pressure. Such

systems do work on the surroundings and therefore some of the
energy supplied to them as heat escapes back to the surroundings.
As a result, the temperature of the system rises less than when the
heating occurs at constant volume.
A smaller increase in temperature implies a larger heat capacity, so

we conclude that in most cases the heat capacity at constant
pressure of a system is larger than its heat capacity at constant
volume.
Simple relation between the two heat capacities of a perfect gas:
20
Adiabatic changes
Changes that occur when a perfect gas expands adiabatically is
discussed.
A decrease in temperature should be expected: because work is

done but no heat enters the system, the internal energy falls, and
therefore the temperature of the working gas also falls. In molecular
terms, the kinetic energy of the molecules falls as work is done, so
their average speed decreases, and hence the temperature falls.
Fig. 14 To achieve a change of state from one temperature and

volume to another temperature and volume, we may consider the
overall change as composed of two steps. In the first step, the system
expands at constant temperature; there is no change in internal
energy if the system consists of a perfect gas. In the second step, the
temperature of the system is reduced at constant volume. The overall
change in internal energy is the sum of the changes for the two steps.
21
The change in internal energy of a perfect gas when the temperature

is changed from Ti to Tf and the volume is changed from Vi to Vf can
be expressed as the sum of two steps (Fig. 14).
First step:
Second step:
22
The initial and final temperatures of a perfect gas that

undergoes reversible adiabatic expansion
Problem:
Consider the adiabatic, reversible expansion of 0.020 mol Ar, initially

3 3
at 25°C, from 0.50 dm to 1.00 dm . The molar heat capacity of argon
−1 −1
at constant volume is 12.48 J K mol , what is the work done?
Solution:
23
The pressure of a perfect gas that undergoes reversible adiabatic

expansion from a volume Vi to a volume Vf is related to its initial
pressure by:
The curves of pressure versus volume for adiabatic change are

known as adiabats, and one for a reversible path is illustrated in Fig.
γ
15. Because γ > 1, an adiabat falls more steeply (P ∝ 1/V ) than the
corresponding isotherm (P ∝ 1/V).
The physical reason for the difference is that, in an isothermal

expansion, energy flows into the system as heat and maintains the
temperature; as a result, the pressure does not fall as much as in an
adiabatic expansion.
24
Problem:
5
When a sample of argon (for which γ = /3) at 100 kPa expands
reversibly and adiabatically to twice its initial volume, what is the final
pressure?
Solution:
25
The Second Law
Some things happen naturally; some things don’t.
Thermodynamics is silent on the rate at which a spontaneous change

in fact occurs, and some spontaneous processes (such as the
conversion of diamond to graphite) may be so slow that the tendency
is never realized in practice whereas others (such as the expansion
of a gas into a vacuum) are almost instantaneous.
Spontaneous changes are always accompanied by a dispersal of

energy.
One statement was formulated by Kelvin: “No process is possible in

which the sole result is the absorption of heat from a reservoir and its
complete conversion into work.”
The entropy of an isolated system increases in the course of a

spontaneous change:
Thermodynamically irreversible processes (like cooling to the

temperature of the surroundings and the free expansion of gases) are
spontaneous processes, and hence must be accompanied by an
increase in total entropy.
The thermodynamic definition of entropy

The thermodynamic definition of entropy concentrates on the change
in entropy, dS, that occurs as a result of a physical or chemical
change (in general, as a result of a ‘process’).
A change in the extent to which energy is dispersed depends on how

much energy is transferred as heat.
Heat stimulates random motion in the surroundings. On the other

hand, work stimulates uniform motion of atoms in the surroundings
and so does not change their entropy.
26
dqrev
dS =
T
For a measurable change between two states i and f this expression

integrates to
f dqrev
∆S = ∫
i T
To calculate the difference in entropy between any two states of a

system, a reversible path between them is adopted. Integrate the
energy supplied as heat at each stage of the path divided by the
temperature at which heating occurs.
27
Example:
Calculate the entropy change of a sample of perfect gas when it

expands isothermally from a volume Vi to Vf.
Answer:
28
Consider an infinitesimal transfer of heat dqsur to the surroundings.

The surroundings consist of a reservoir of constant volume, so the
energy supplied to them by heating can be identified with the change
in their internal energy, dUsur.
The internal energy is a state function, and dUsur is an exact

differential. So, dUsur is independent of how the change is brought
about and in particular is independent of whether the process is
reversible or irreversible.
29
When a chemical reaction takes place in a system in thermal

equilibrium with its surroundings (Tsur = T),
Calculation:
Calculate the entropy change in the surroundings when 1 mol of H2O

(l) is formed from its elements under standard conditions at 298.15K.
(given that : ΔHfθ (H2O, l) = - 286 kJ)
Answer:
30
The statistical view of entropy
Entropy is the degree of disorder in a system.

The perfectly ordered system has zero entropy.
The less perfectly ordered system has higher entropy.
The expansion of perfect gas
The change in entropy of a perfect gas that expands isothermally

form Vi to Vf is
V
∆S = nR ln f
Vi
Because S is a state function, the value of ∆S of the system is

independent of the path between the initial and final states, so this
expression applies whether the change of state occurs reversibly or
irreversibly.
The total change in entropy, however, does depend on how the

expansion takes place. For any process dqsur = −dq, and for a
reversible change:
qsur q V
∆S sur = = − rev = −nR ln f
T T Vi
∆Stot = 0 (reversible process)
Isothermal expansion occurs freely (w = 0) and irreversibly
31
The entropy of phase transition temperature
A change in the degree of molecular order occurs when a substance

freezes or boils, we should expect the transition to be accompanied
by a change in entropy.
e.g. when a substance vaporizes, a compact condensed phase

changes into a widely dispersed gas. So, the entropy of the
substance increases.
A phase transition at the transition temperature under 1 atm pressure

is a reversible isothermal process. The entropy change of the system:
∆ H
∆S = trs
Ttrs
e.g.
1) at 273 K (0 oC) for ice in equilibrium with water at 1 atm
2) at 373 K (100 oC) for water in equilibrium with its vapor at 1 atm
32
The variation of entropy with temperature
Calculate the entropy of a system at a temperature Tf from its entropy

at a temperature Ti and the heat supplied to change its temperature
from one value to the other:
33
Example:
Calculate the entropy change when argon at 25 oC and 1.00 atm in a

container of volume 500 cm3 is allowed to expand to 1000 cm3 and is
simultaneously heated to 100 oC. (Cv = 12.47 J K-1 mol-1)
Anwser:
34
Third Law
At T = 0, all energy of thermal motion has been quenched, and in a

perfect crystal all the atoms or ions are in a regular, uniform array.
The localization of matter and the absence of thermal motion suggest
that such materials also have zero entropy.
S = 0 if there is only one way of arranging the molecules (the ground

state).
The entropy change accompanying any physical or chemical

transformation approaches zero as the temperature approaches zero:
∆S → 0 as T → 0 provided all the substances involved are perfectly
crystalline.
If the value zero to the entropies of elements in their perfect

crystalline form at T = 0 is ascribed, then all perfect crystalline
compounds also have zero entropy at T = 0.
Third Law of thermodynamics:
“The entropy of all perfect crystalline substances is zero at T = 0.”
As far as thermodynamics is concerned, choosing this common value

as zero is then a matter of convenience. (S = 0 at T = 0)
Third-Law entropies
S(0) = 0 --- (Third-Law entropies or just ‘entropies’)
S (T) denotes standard (Third-Law) entropy when the substance is in

its standard state at the temperature T.
35
The standard reaction entropy (∆rS ) is defined as the difference

between the molar entropies of the pure, separated products and the
pure, separated reactants, all substances being in their standard
states at the specified temperature:
= ∑ nS θ (products) − ∑ nS θ (reactants)
θ
∆rS
36
Calculation
Calculate the standard entropy of H2 (g) + ½ O2 (g) → H 2O (l) at 25

o
C.
Given: Sθ (H2, g) = 130.7 J K-1 mol-1

Sθ (O2, g) = 205.0 J K-1 mol-1
Sθ (H2O, l) = 69.9 J K-1 mol-1
Answer:
37
The Helmholtz* and Gibbs energies
Consider a system in thermal equilibrium with its surroundings at a

temperature T. When a change in the system occurs and there is a
transfer of energy as heat between the system and the surroundings,
the Clausius inequality reads
dq
dS − ≥0
T
Criteria for spontaneity
Consider heating at constant volume and in the absence of non-

expansion work.
dqV = dU
dU
dS − ≥0
T
TdS ≥ dU (V = constant, no additional work)
Note: ‘additional work’ is work other than expansion work.
At either constant internal energy (dU = 0) or
constant entropy (dS = 0):
dS U, V ≥ 0 dU S, V ≤ 0
and
Interpretations:
1. The first inequality ( dS U, V ≥ 0 ) states that, in a system at
constant volume and constant internal energy (such as an
isolated system), the entropy increases in a spontaneous
change.
2. The second inequality ( dU S, V ≤ 0 ) states that, if the
entropy and volume of the system are constant, then the
internal energy must decrease in a spontaneous change.
38
When energy is transferred as heat at constant pressure, and there is

no work other than expansion work:
dqp = dH
TdS ≥ dH (P = constant, no additional work)
At either constant enthalpy (dH = 0) or
constant entropy (dS = 0):
dS H, P ≥ 0 dH S, P ≤ 0
and
Interpretations:
1. The entropy of the system must increase if its enthalpy
remains constant (for there can be no change in entropy
of the surroundings).
2. The enthalpy must decrease if the entropy of the system
is constant, for then it is essential to have an increase in
entropy of the surroundings.
39
Helmholtz energy* (A) which is defined as
A = U - TS
Gibbs energy (G)
G = H – TS
When the state of the system changes at constant temperature:
dA = dU – TdS (if the change is infinitesimal)*
ΔA = ΔU – TΔS (if it is measurable)*
and
dG = dH – TdS (if the change is infinitesimal)
ΔG = ΔH – TΔS (if it is measurable)
So, the criteria of spontaneous change as

dAT,V ≤ 0*
and
dGT,P ≤ 0
These inequalities are the most important conclusions from

thermodynamics for chemistry.
40
Some remarks on the Gibbs energy
The Gibbs energy (the ‘free energy’) is more common in chemistry

than the Helmholtz energy because more interest in changes
occurring at constant pressure than at constant volume. T
The criterion dGT,p ≤ 0 is spontaneous in the direction of decreasing

Gibbs energy.
If G decreases as the reaction proceeds, then the reaction has a

spontaneous tendency to convert the reactants into products. If G
increases, then the reverse reaction is spontaneous.
Spontaneous endothermic reactions:
dH > 0 (endothermic reaction)
dG < 0 (spontaneous reaction)
and dG = dH − TdS
The entropy of the system increases so much that TdS outweighs dH

in dG = dH − TdS.
Endothermic reactions are therefore driven by the increase of entropy

of the system, and this entropy change overcomes the reduction of
entropy brought about in the surroundings by the inflow of heat into
the system (dSsur = −dH/T at constant pressure).
41
Standard molar Gibbs energy of reaction
θ
∆ r G = ∑ nG θ (products) − ∑ nG θ (reactants)
θ
∆ r G θ = ∆ r H θ − T∆ r S
Calculation
Calculate the standard reaction Gibbs energy for

CO (g) + ½ O2 (g) → CO2 (g) at 25 oC.
Given: Gθ (CO, g) = -137.2 J mol-1

Gθ (O2, g) = 0 J mol-1
Gθ (CO2, g) = -394.4 J mol-1
Answer:
42
Physical Chemistry II – Electrochemistry Prepared by Chan Chin Han
Electrochemistry (CHM 520)
Faraday’s Laws of Electrolyisis (Electrolytic Deposition)
Faraday studied the quantitative relationships between amount of

current and amount of material released from solution. His results are
stated in two laws of electrolysis:
1
Electrolytic Conduction
Terminology
The fundamental measurement used to study the motion of ions is

that of the electrical resistance (R) of the solution.
The basic electrical quantities are current (I), potential (V), and
resistance (R), with units of ampere (A), volt (V), and ohm (Ω),
respectively.
These quantities are related by Ohm’s law:
∆V
R=
I
Conductance and conductivity
Conductance (G) (Ω-1, is called siemens, S)

= reciprocal of the resistance
The conductance of a sample decreases with its length l and

increases with its cross-sectional area A:
2
1 A A
G= ∝ =κ
R l l
A = cross-sectional area
l = length of the medium
−1
κ = electrolytic conductivity (S m ) (in the case of a solution of an
electrolyte)
For electrolytic conductivity (κ), whose SI units is S m-1 (or Ω-1 m-1),
the values of κ increase with temperature and concentration.
Note:
Molar conductivity (Λ ) :
The conductivity of a solution depends on the number of ions present,

and it is normal to introduce (Λ )
κ  Ω −1 m −1 
Λ=  
−3 
C  mol m 
Imagine two electrodes held at a separation of 1 m. If a solution has a

concentration C (mol m-3), then the volume of solution containing one
mole = 1/C m3 and both electrodes would have to have an area 1/C
m2, for a separation of 1 m.
3
Λ is found to vary with the concentration. Reasons:
4
Calculation:
The molar conductivity of 0.0050 M KCl is 144 Ω-1 cm2 mol-1.

Calculate its electrolytic conductivity in SI units.
Solution:
5
Measurement:
Bridge circuit for conductivity determination.
R2
R1
D
R3
A: Conductivity cell
B: Oscillator
C: Capacitance (variable) to balance capacitance of cell.
D: Detector
6
The conductivity of a solution is measured in a cell that is one arm of

a Wheatstone bridge. They actually measure resistance. The
electrolytic conductivity is calculated from:
1l 
κ=  
R  A
since l and A are difficult to measure, the usual procedure is to treat
l/A as a cell constant and to calibrate the cell by using of KCl, having
a known molar conductivity. Then
1
κ= K cell
R
Calculation:
A student measured the resistance of a 0.100 M NaCl solution to be

19.9 Ω. Calculate the experimental value of the molar conductivity of
this solution. (cell constant, Kcell = 0.2120 cm-1)
Solution:
7
The concentration dependence of Λ indicates that there are two

classes of electrolyte.
1. strong electrolyte:
2. weak electrolyte:
Strong electrolytes
Strong electrolytes are substances that are virtually fully ionized in

solution, and include ionic solids and strong acids. As a result of their
complete ionization, the concentration of ions in solution is
proportional to the concentration of strong electrolyte added.
e.g. solution of salt, strong mineral acids and alkalis, quaternary salts
of amines and etc.
Friedrich Kohlrausch showed that at low concentrations:
Note:
For weak electrolyte, the above equation is not valid approach C =
0 because, the extrapolation is unreliable (almost asymptotic
approach of the curve to the y axis).
8
Consider a strong electrolyte that yields ions A and B in solution,

according to
ApBq → pAz+ + qBz-
Kohlrausch assumed that in such a system the molar conductivity at

infinite dilution is simply the sum of the independent contribution of
the ions.
Kohlrausch’s law of independent migration of ions:
This equation has been written for infinite dilution since it is only
under such conditions, when ion-ion interactions are at a minimum
that the law strictly holds.
It is then applicable to both strong and weak electrolytes.
9
Weak electrolytes
Weak electrolytes are not fully ionized in solution. They include weak
Brønsted acids and bases, such as CH3COOH and NH3. The marked
concentration dependence of their molar conductivities arises from
the displacement of the equilibrium towards products at low molar
concentrations.
The conductivity depends on the number of ions in the solution.
For weak acids (HA) at a molar concentration c, at equilibrium

with degree of ionization ( ) of the electrolyte:
10
Problem:
The molar conductivity of 0.0100 m CH3COOH (aq) at 298 K is Λ =

2 −1
1.65 mS m mol . What is the acidity constant (Ka) of 0.0100 m
CH3COOH (aq).
Solution:
11
Ostwald/s dilution law (for weak electrolyte at diluted concentration)
Fig. 2 The graph used to determine the limiting value of the molar
conductivity of a solution by extrapolation to zero concentration.
This equation implies that, if 1/ Λ is plotted against c Λ , then the
intercept at c = 0 will be 1/ Λ o .
12
Relation between an ion’s mobility and its molar ionic

conductivity
13
Ion’s Velocity
The individual and independent conductivities of ions, postulated by

Kohlrausch ( Λ o = pλ+ ,o + qλ− ,o ) are determined by the velocities of
those ions.
The speed of an ion as it moves under the influence of an electric

field is called its mobility, u.
Question:
What are the SI units of mobility?
Solution:
14
Transport numbers
Since the cation and anion usually have different mobilities, they
usually carry different fraction of the current.
The fraction of the current carried by an ion is called the transport

number, t, of that ion.
The transport number is simply a current fraction, which is analogous

to a mole fraction. For strong electrolytes ApBq, with concentration of
the solution is c, the concentration of cations is pc and the current I+
carried by cations through a unit area A in unit time is z+u+pcFEA. We
substitute:
I+ = z+u+pCFEA for I+ and the equivalent term for I-.
We obtain:
15
Calculation:
The mobilites of K+ and acetate ion are 7.61 X 10-4 and 4.23 X 10-4
cm2 V-1 s-1, respectively, at 25 oC. What are their transport numbers in
potassium acetate solution?
Solution:
16
We can determine transport numbers by several methods, e.g. Hittorf

method and moving boundary method. (These won’t be discussed
further)
The importance of transport numbers is that they give a simple way to

obtain molar ionic conductivities. Quantities t and λ are related
through u:
For infinite dilution, Λ o = pλ+ ,o + qλ− ,o (Kolhrausch):
17
Calculation:
The transport numbers of K+ and AC- in a KAc solution are t+ = 0.643,

t- = 0.357. If an experiment yields 114.3 Ω-1 cm2 mol-1 as the value of
Λ o of KAc, what are the experimental molar ionic conductivities at
infinite dilution?
Solution:
18
The activities of ions in solution
For dilute solutions of non-electrolytes, it is generally safe to make

the approximation that solute activities can be replaced by their
molarities
In ionic solutions, the interactions between ions are so strong that this
approximation is valid only in very dilute solutions (< 10-3 mol/kg total
ion concentration) and, in precise work, activities themselves must be
used.
The definition of activity
The chemical potential of a solute in a real solution is related to its

activity a by:
19
20
Mean activity coefficients
Total Gibbs energy of ions in the electrically neutral solution is the

sum of these partial molar quantities. The Gibbs energy of an ideal
solution is:
All the deviations from the ideality are contained in the last term.
There is no experimental way of separating the product γ+γ- into

contributions from the cations and the anions.
The best we can do experimentally is to assign responsibility for the

non-ideality equally to both kinds of ion.
21
The sum of these two chemical potentials is the same as before, but
now the non-ideally is shared equally.
To the case of a compound MpXq that dissolves to give a solution of p

cations and q anions. The total Gibbs energy of the ions:
22
The Debye–Hückel limiting law
The long range and strength of the Coulombic interaction between

ions means that it is likely to be primarily responsible for the
departures from ideality in ionic solutions and to dominate all the
other contributions to nonideality.
This domination is the basis of the Debye–Hückel theory of ionic

solutions, which was devised by Peter Debye and Erich Hückel in
1923.
Oppositely charged ions attract one another. As a result, anions are

more likely to be found near cations in solution, and vice versa (Fig.
3). Overall, the solution is electrically neutral, but near any given ion
there is an excess of counter ions (ions of opposite charge).
The environment of a particular ion therefore carries an opposite

charge, and this diffuse, charged environment is known as the ionic
atmosphere.
The energy of a solution of ions distributed in this way will differ from
that of purely random arrangement, and this different energy will be
contribution to the Gibbs free energy of the ions in solution.
The electrical and chemical behavior of ions is determined

thermodynamically by their free energy, and so the dependence of
free energy on concentration is important for both practically and
theoretically.
The calculation of the free energy of an ionic solution by the Debye-

Hückel theory of strong electrolytes is involved.
23
Some of the assumptions:
The energy, and therefore the chemical potential, of any given central
ion are lowered as a result of its electrostatic interaction with its ionic
atmosphere.
This lowering of energy appears as the difference between the Gibbs

energy G and the ideal value Gid of the solution, and hence can be
identified with RT ln γ ± .
24
At very low concentrations, the activity coefficient can be calculated

from the Debye-Hückel limiting law:
25
Calculation:
Estimate the mean activity coefficient of 0.005 M KCl (aq) at 25 oC?
Solution:
26
Debye–Hückel–Onsager theory*
Modification of Onsager and others have extended the range of

concentration to higher concentration for Debye-Hückel limiting law.
When an electrical potential is applied across a solution, two effects

produced by the ionic atmosphere prevent the ion from moving at the
expprected speed and hence from conducting the expected amount
of current.:
27
Ionic Equilibria
Equilibrium (plural – equilibria) is usually established very

rapidly between ionic species in solution.
Activity coefficients can be determined when equilibria are

established in solution.
Activity coefficients from equilibrium
Dissociation of acetic acid:
CH3COOH H+ + CH3COO-
28
29
Solubility products
Salt and its saturated solution, e.g.
AgCl (s) Ag+ (aq) + Cl- (aq)
30
For sparingly soluble uni-univalent salt AB:
AB (s) A+ (aq) + B- (aq)
31
Equilibrium electrochemistry
Electrochemical Cells
A cell consists of two electrodes, in contact with an electrolyte, and

ionic conductor.
An electrode and its electrolyte comprise an electrode compartment.

The two electrodes may share the same compartment.
If the electrolytes are different, the two compartments may be joined

by a salt bridge.
Salt bridge – concentrated electrolyte solution in agar jelly that

completes the electrical circuit and enables the cell to function.
Galvanic cell – an electrochemical cell that produces electricity as a

result of the spontaneous reaction occurring inside it.
Electrolytic cell – an electrochemical cell in which a non-spontaneous

reaction is driven by an external source of current. (have a common
electrolyte and no salt bridge.
32
Electrode
Electrolyte
A cell with a single electrode compartment and a shared electrolyte.
Electrode
Salt Bridge
Electrode
compartment
Two separate electrode compartments joined by a salt bridge.

Half-reactions and electrodes
33
34
A redox reaction is a reaction in which there is a transfer of electrons

from one species to another.
Reducing agent / reductant – is the electron donor.
Oxidizing agent / oxidant – is the electron acceptor.
Examples of redox reactions:

1) 2 Mg (s) + O2 (g) → 2 MgO (s)
Mg –
O2 –
2) CuO (s) + H2 (g) → Cu (s) + H2O (g)
H2 –
CuO –
3) Cu2+ (aq) + Zn (s) → Cu (s) + Zn2+ (aq)
Zn –
Cu2+ –
Half-reactions:
The reduction of Cu2+ ions by zinc can be expressed as the sum of

the following 2 half-reactions:
Reduction of Cu2+:
Oxidation of Zn :
Overall :
It is a common practice that to write all half-reactions as reductions.
The reduced and oxidized substances in a half-reactions form a

redox couple, denoted Ox/Red. (e.g. Cu2+/Cu, Zn2+/Zn)
The corresponding reduction half-reactions as:

Ox + ne → Red
35
Reaction Quotient, Q
For half-reaction:
The reaction quotient for the reduction of O2 to H2O in acid solution:
36
Reactions at electrodes
Electron
Anode Cathode
Oxidation
Reduction
When a spontaneous reaction takes place in a galvanic cell, electrons

are deposited in anode (oxidation) and collected from cathode
(reduction). So, there is a net flow of current that can be used to do
work.
37
In galvanic cell, the cathode has a higher potential than the anode:
The species undergoing reduction, withdraws electrons from its

cathode, so leaving a relative positive charge on the cathode.
(higher potential)
At the anode, oxidation results in the transfer of electrons to the
electrode, so giving it a relative negative charge (lower
potential).
In an electrolytic cell, anode is relatively positive to cathode:
The anode is also the location of oxidation (by definition), but

now electrons must be withdrawn from the species in that
compartment since that process does not occur spontaneously.
At the cathode there must be a supply of electrons to drive the
reduction (relatively positive charge).
38
Varieties of electrodes:
Metal / metal ion electrode:
Cu electrode Electrode reaction

Cu2+ + 2 e- ↔ Cu
39
Redox electrode:
40
Gas electrode:
• A gas in equilibrium with a solution of its ions in the presence of

an inert metal.
• E.g.: Hydrogen electode (hydrogen is bubbled through a
solution of hydrogen ions)
41
Using the standard hydrogen electrode:
The standard hydrogen electrode is attached to the electrode system

you are investigating - for example, a piece of magnesium in a
solution containing magnesium ions.
42
Metal │ insoluble-salt electrode:
43
Notation for cell:
Phase boundaries denoted by a vertical bar.
e.g.
A liquid junction is denoted by  .
e.g.
A double vertical line││ denotes an interface for which it is

assumed that the junction potential has been eliminated (by
joining the electrolyte compartments through a salt bridge).
e.g.
44
The cell reaction:
The cell reaction is the reaction in the cell written on the assumption
that the right-hand electrode is the cathode, and hence that the
spontaneous reaction is one in which reduction is taking place in the
right-hand compartment.
For example:
The reduction of Cu2+ ions by zinc:
Reduction of Cu2+:
Oxidation of Zn :
Overall :
So,
Right :
Left :
Overall:
Thus, in the cell,
45
Varieties of cells
1. ‘Daniell cell’ –
2. Electrolyte concentration cell –
3. Electrode concentration cell –
Fig. 5 One version of the Daniell cell. The copper electrode is the
cathode and the zinc electrode is the anode. Electrons leave the cell
from the zinc electrode and enter it again through the copper
electrode.
46
The cell potential:
The potential difference between the two electrodes is called
A cell in which the overall cell reaction has not reached chemical
equilibrium can do electrical work as the reaction drives electrons
through an external circuit.
A cell in which the overall reaction is at equilibrium can do no work,

and then the cell potential is zero.
The relation between E and ΔrG:
Background (thermodynamics - Gibbs free energy)
That is, the maximum non-expansion work we can obtain from a

process at constant pressure and temperature is given by the value
of ΔG for the process.
47
Application in electrical work:
The maximum electrical work that a cell can do is given by the value
of ΔG and, in particular, that, for a spontaneous process.
wmax = ΔG (T,p = constant)
Therefore, to measure ΔG we must ensure that the cell is operating

reversibly at a specific, constant composition.
Both of these conditions are achieved by measuring the cell potential

when it is balanced by an exactly opposing source of potential so that
the cell reaction occurs reversibly and the composition is constant.
The resulting potential difference is called the zero-current cell

potential, E (or electromotive force, emf, of the cell).
The voltmeter
Voltmeter has high resistance and ideally, it wants to have an

infinitely high resistance. This is to avoid any flow of current through
the circuit.
If any current flows, the voltage measured drops. In order to make

proper comparisons, it is important to measure the maximum possible
voltage in any situation. This is called the electromotive force ( emf).
The emf of a cell measured under standard conditions is given the

symbol Eθ.
48
The Nernst Equation
49
Standard Potentials
We can define the potential of one of the electrodes as having a zero

potential and then assign values to others on that basis.
The specially selected electrode is the standard hydrogen electrode

(SHE) (is the left-hand electrode).
Pt │ H2 (g) │ H+ (aq) Eθ = 0 at all temperatures
Example:
The standard potential of the Ag+/Ag couple (is the right-hand
electrode):
The standard potential of the AgCl/Ag,Cl- couple (is the right-hand

electrode):
Half-reaction:
Overall reaction:
50
Standard cell potential and standard potential are intensive properties

and are unchanged if the chemical equation for the cell reaction or a
half-reaction is multiplied by a numerical factor.
51
Concentration cell
The cell:
M │ M+ (aq, L) ││ M+ (aq, R) │ M
Solutions L and R have different molarities. Concentration R > L.
If R is the more concentrated solution, then E > 0. Physically, the

positive potential arises because positive ions tend to be reduced,
thus withdrawing electrons from the electrode, and this process is
dominant in the more concentrated right-hand electrode compartment.
The cell reaction:
52
Cell at equilibrium
Suppose the reaction has reached equilibrium; then Q = K.
K = equilibrium constant of the cell reaction.
The cell:
A chemical reaction at equilibrium cannot do work and hence it

generates zero potential difference between the electrodes of a
galvanic cell.
Cell reaction:
For example: the standard potential of the Daniell cell is:
Zn (s) │ ZnSO4 (aq) ││ CuSO4 (aq) │ Cu(s) Eθ = + 1.10 V
53
Example:
One of the reactions important in corrosion in an acidic environment

is
Fe (s) + 2 H+ (aq) + ½ O2 (g) → Fe2+ (aq) + H2O (l)
Does the equilibrium constant favor the formation of Fe2+ (aq)?
Solution:
54
The composition dependence of individual potentials
The potential of an Ag+/Ag electrode is given by the expression
Ag+ (aq) + e → Ag (s),
Problem:
Chlorine gas is bubbled over a platinum electrode dipping into

aqueous sodium chloride at 298K. Calculate the change in the
potential of the electrode when the chlorine pressure is increased
from 1.0 atm to 2.0 atm. (RT/F = 25.69 mV)
Solution:
55
56
Redox Electrode
Fe3+ (aq) + e → Fe2+ (aq)
3+ 2+ θ
E (Fe , Fe ) = E (Fe , Fe ) −
RT a Fe 2+
3+ 2+ ( )
F
ln
a Fe3+ ( )
This equation implies that an increase in Fe3+ tends to increase the
electrode potential and increase in Fe2+ tends to lower it.
We can control the equilibrium by modifying the electrode potential. In

other words, we can use electrical control over the composition of
solutions.
57
The measurement of standard reduction potentials
Harned cell
Pt │ H2 (g) │ HCl (aq) │ AgCl (s) │ Ag (s)
58
59
Problem:
Determining the standard emf of a cell.
The emf of the cell Pt(s) | H2 (g, p ) | HCl (aq, b) | AgCl (s) | Ag (s) at
25°C has the following values:
Solution:
60
The measurement of activity coefficient
Once the standard potential of an electrode in a cell is known, the

activities of the ions with respect to which it is reversible can be
determined simply by measuring the cell potential with the ions at the
concentration of interest.
Application of standard potential: (1) Solubility constants
For a sparingly soluble salt MX in terms of equilibrium,
MX (s) <----> M+ (aq) + X-
61
Application of standard potential: (2) The measurement of pH.
The potential of a hydrogen electrode

2 H+ (aq) + 2e → H2 (g)
62
Physical Chemistry II – Radiochemistry Prepared by Chan Chin Han
RADIOCHEMISTRY (CHM 520)
Radiochemistry may be defined as the study of the chemistry of

atoms which have radioactive nuclei.
A radioactive atom will at some time undergo radioactive decay

enables us to carry out certain experiments which would be difficult or
impossible with only non-active atom.
Radioactivity was discovered by Becquerel when investigating

fluorescence in uranium compounds. (1896)
Chemical properties of different isotopes of an element
Nuclear properties
Radioactivity, or radioactive decay,
Nuclide -
Nucleons -
1
2
The nature of the radiations from radioactive substances
γ
α
β
Source
The effect of a magnetic field perpendicular to the page on various

types of radiation.
3
Rutherford identified 2 different types of radiation.
(a) alpha ray (α)

- Alpha rays caused very dense ionization, but were easily
stopped, by a piece of thick paper for instance.
- The charge/mass ratio of alpha particle was half that of
the proton.
- Was a doubly ionized helium atom, He2+, which has a
mass number of 4 (2 protons and 2 neutrons).
- If the nucleus of a neutral atom emits an alpha particle
(2p + 2n), it loses 2 positive charges and electrical
neutrality is maintained by a following loss of 2 orbital
electrons.
- Thus, the atom moves 2 places down the periodic table
and at the same time loses 4 units of mass.
238 α 234
U Th
t 12 = 4.5 × 10 y
92 9 90
226 α 222
Ra Rn
t 12 = 1600 y
88 86
4
(b) beta ray (β)

- Beta rays caused much less ionization, but could
penetrate matter much more easily.
- The charge/mass ratio of beta rays was the same as that
of the electron, and in fact beta rays are simply very
energetic electrons.
- β-decay with subdivision of β- -decay ( −10 e ) , β+ - decay
0
( 1 e ) and electron capture.
- In beta decay no mass is lost since the electron mass is
negligible compared to the nuclear mass, but the loss of a
negative charge by the nucleus is equivalent to the gain
of a positive charge and the atom therefore moves up one
place in the periodic table.
e−
2 He + v
3 3
H
t 12 = 12.3y
1
e−
16 S + v
32 32
P
t 12 = 14.1d
15
5
In the meantime, a third type of radiation called gamma radiation (γ)

was recognized.
- it was found to be undeflected by a magnetic field.
- Is electromagnetic radiation of very short wavelength≈ (
10-12 m) compared to visible light ≈ (10 -7 m) or radio
waves (≈ 102 m).
- The nucleus is initially present in a higher energy state
(excited state, ex) and decay occurs when this excited
state drops to the ground state (g) or to a lower excited
state.
In general:
6
Example:
Radon-222 is enclosed in capsules as a radiation source for

treatment of some types of cancer; phosphorus-32 is used to label
red blood cells for blood volume determinations; aluminum-28 is
produced in the bombardment of aluminum-27 by neutrons. Write a
nuclear equation for
(a) α-particle emission by radon-222,
(b) β– decay of phosphorus-32,
(c) γ decay of aluminum-28.
Solution:
7
8
9
Nuclear Binding Energy
Nuclear binding energy:
Although the energy is released, binding energy is expressed as a

positive quantity.
Mass defect (∆m) –
Einstein’s mass-energy equivalence relationship:
10
Atomic mass unit (amu):
The chart below shows the masses of fundamental particles of

matter:
Particle Mass (amu) Charge

electron 0.00054858 -1
proton 1.0073 +1
neutron 1.0087 neutral
11
Problem:
Consider an atom of rubidium-87 which a mass deficiency (∆m) of

0.816 amu. Calculate the nuclear binding energy (BE) for this atom.
Solution:
12
In order to compare the stability of any two nuclei, we must account

for the fact that they have different numbers of nucleons.
So, nuclear binding energy per nucleon is more relevant in this case.
13
The rate of decay of radioactivity
We found that the radioactivity of the gas decayed with time; in the
case of radon, the decay curve is shown as below:
% of maximum activity
100
(b)
50
(a)
3.8 days Time / days
(a) Decay of radon separated from radium

(b) Growth of radon in an initially pure sample of radium
The activity decreased in such a way that it reached one half of its
value after 3.8 days.
Thus, after 3.8 days it was 50 % of its initial value, after 7.6 days,
25 % and so on.
All known radioactive species have been found to decay in this

manner.
Half-life (t½) is the time required for a radioactive atom to reach one
half of its initial activity. This quantity is the characteristic of the
particular radioactive substance.
14
Assumption:
Radioactibvity (A):
Radioactive decay rate:
15
Relation between λ and t½
Knowledge of the half-life (or the decay constant) is most useful if we

wish to identify a particular radioactive species.
16
Radiochemical equilibrium
When the half-life of a parent is long is comparison with that of its

daughter, a steady-state is achieved after the lapse of a considerable
time, in which the daughter element decays as fast as it is produced.
A constant amount of the daughter element is present in equilibrium

with the parent.
17
Example: 238U
α β- β-
238
U ----------> 234Th ----------> 234Pa ----------> 234U
t½ = 4.5 x 109 y t½ = 24.1 d t½ = 1.18 m
Parent Daughter Grandchild Great-grandchild
18
Nuclear reactions
Nuclear reactions are similar in many ways to chemical reactions.

The main differences are:
19
Nuclear Fission
2 types of fission of heavy atomic nuclei into 2 nearly equal fragments

may be distinguished.
1) Spontaneous fission, where the nucleus undergoes fission

without external influence (e.g. without introduction of energy).
2) Induced fission, where the decay of an energetically excited
nuclear state through fission and is a particular form of energy
loss from an excited compound nucleus.
Heavy nuclei undergo fission as a result of bombardment by protons,

α-particles or other charged particles.
Most important type of nuclear fission is that brought about by

neutrons, which as uncharged particles experience no repulsion from
the target nucleus.
Although fission usually yields 2 fragments, in a few cases, fission

into three fragments has been observed, the third fragment being a
light particle (3H, 4,6,8He, 6Li or 10Be).
20
Reaction of 235U with thermal neutrons
When a thermal neutron collides with a 235U nucleus, the neutron is

captured and forms a highly excited compound nucleus,
235
U + n → (236U)*
The compounds nucleus (t½ ≈ 10-14 s) must now lose its excitation
energy. This it can do through γ-emission or through fission.
(236U)* → 1) 2 fission products + v neutrons.

Or → 2) 236U + γ-quanta
Every 7 235U nuclei have captured a thermal neutron, about 6 will

undergo fission and one will decay to the ground state of the long-
lived 236U, whereby the excitation energy is emitted in the form of γ-
quanta.
e.g.
( 236
92 )
U *→139
54 Xe + 38 Sr
97
21
Nuclear Fusion
Binding energy is released from the fusion of light atomic nuclei. Only
the fusion of hydrogen isotopes to helium has up to now been
investigated.
41 H→4 He + 2e + + 2v
D+ 6 Li →24 He
1
0 n + 63 Li→42 He+ 31H
22
Nuclear radiation detector
i) Gas counters
The simplest type in principle and is illustrated schematically

as below.
The ions and electrons produced by the incident radiation

move in the electric field to the electrodes and produce there
a current. The current is measured by a sensitive ammeter.
Disadvantage: it can only be used with very strong sources,

since the current is very small ≈10 ( -15
A) and difficult to
measure accurately. (If the saturation potential is reached,
all the charge carriers are discharged and a constant current
is obtained which is independent of any further increase in
potential.
Current
Ammeter
- A
Electrode
+
-
Source
+
Glass
envelope
23
ii) Proportional counters
The primary electrons become sufficiently accelerated to

cause secondary ionization through collisions with gas
molecules.
Therefore from a primary excited ion pair produced by the

nuclear radiation, a great many ion pairs may be generated,
the number being proportional to the applied potential.
The intensities of the pulses obtained are much greater than

those from the ionization chamber, in which secondary
ionization does not occur.
Methane or argon-methane is used as counting gases for

proportional counters.
High resistance
V Detector
A
Radiation
Voltage supply
24
iii) Geiger-Müller Counters
The setting up of it is similar to proportional counters, with

the applied voltage is increased further.
The number of multiplicative collisions increases that

eventually every gas molecule inside the multiplicative
region will become ionized.
The amount of charge collected at the anode will no longer

depend on the number of primary electrons entering the
multiplicative region, since even one entering electron will
cause complete ionization of the gas in this region.
The size of the output pulse will be very large, and will
depend only on the number of gas molecules in the
multiplicative volume.
Advantage: very large output pulse≈( 10V) with no further

amplification and so the complete counting arrangement is
cheap.
Disadvantages: after a pulse has been registered, the

counter cannot operate until the positive ions have reached
the cathode and been discharged.
This takes about 10-4 s, and during this ‘dead time’ any
pulses which arrive are not counted. To avoid this loss, the
counting rate should be less that about 10,000 counts per
minutes.
25
iv) Scintillation counters
It consists basically of a phosphor material in which the

energy of the incident radiation is converted to light quanta,
which in turn impinge on a photocathode (consists of a metal
or alloy) to release electrons.
The electrons liberated by the light are accelerated to the

first of the multiplying electrodes, called dynodes.
The collision of electrons with dynode releases more

electrons and these pass on to the next dynode.
In most photomultipliers there are 11 or 13 dynodes.

Electrons are amplified in this photomultipliers by a factor of
105 to 107.
This measurable pulse is further amplified before counting.
Because the number of light quanta produced in the

phosphor and thus the number of electrons released at the
photocathode is dependent on the energy of the incident
26
radiation, measurement of both the particle number and the

particle energy is possible.
Advantages: short dead-time, unlimited lifetime, energy

proportionality of pulses.
Disadvantage: rather high cost.
Radiation source
Phosphor
Photo-sensitive cathode
Dynodes Photomultiplier
Detector
Amplifier
27
v) Solid state or semiconductor detectors
A semiconductor detector is a device that uses a

semiconductor (usually silicon or germanium) to detect
traversing charged particles or the absorption of photons (in
particular for gamma and X-ray spectrometry and as particle
detectors).
In these detectors, radiation is measured by means of the

number of charge carriers set free in the detector, which is
arranged between two electrodes.
Ionizing radiation produces free electrons and holes. The

number of electron-hole pairs is proportional to the energy
transmitted by the radiation to the semiconductor. As a
result, a number of electrons are transferred from the
valence band to the conduction band, and an equal number
of holes are created in the valence band.
Under the influence of an electric field, electrons and holes

travel to the electrodes, where they result in a pulse that can
be measured in an outer circuit. The holes travel into the
opposite direction and can also be measured.
As the amount of energy required to create an electron-hole

pair is known, and is independent of the energy of the
incident radiation, measuring the number of electron-hole
pairs allows the energy of the incident radiation to be found.
After the discharge, the original state is regained by diffusion

of free charge carriers, after which the detector is again
ready for use.
28
Advantages: good energy resolution, shorter dead-times.
Disadvantages: particles of very high energy and / or low

specific ionization (e.g. high energy γ-quanta) are not fully
absorbed in the detector volumes (max 100 cm3) available at
the present time.
29
Applications of radioactive nuclides:
Radioisotopes are widely used in medical diagnosis and therapy.
Many of the medically useful radioisotopes have very short half-lives.

Although ionizing radiation can induce cancer, it can also be used to
treat cancer. Cancer cells are destroyed more easily by radiation
than are healthy, normal cells.
In some instances, radioactive chemicals (called

radiopharmaceuticals) can be ingested and allowed to find their own
way to the targeted tissue.
Problem:
1. Iodine-131 is used to destroy thyroid tissue in the treatment of
an overactive thyroid. The half-life of iodine-131 is 8 days. If a
hospital receives a shipment of 200 g of iodine-131, how much
I-131 would remain after 32 days?
[12.5 g]
2. Technetium-99m is used for brain scans. If a laboratory

receives a shipment of 200 g of this isotope and after 24 hours
only 12.5 g of this isotope remain, what is the half-life of
technetium-99m?
[6 hrs]
3. Mercury -197 is used for kidney scans and has a half-life of 3

days. If the amount of mercury-197 needed for a study is 1.0
gram and the time allowed for shipment is 15 days, how much
mercury-197 will need to be ordered?
[32 g]
30
31
Radioactive tracers:
Radioactive nuclides can be used as tracers, and their atoms can be
attached to other substances, which are then said to be “tagged.”
The fate of these “tagged” substances can be tracked with a radiation

detector.
These tracers can be used to:

• Detect leaks in underground piping systems.
• Determine frictional wear in piston rings.
• Determine the uptake of phosphorus and its distribution in
plants.
• Examine transmission of drugs from mother to fetus.
• Elucidate reaction mechanisms.
Radiocarbon dating
14
C is formed at a nearly constant rate in the upper atmosphere by
the bombardment of 14N with neutrons from cosmic radiation.
The 14C is eventually incorporated into atmospheric CO2.
Since atmospheric CO2 eventually finds its way into living tissue, the
level of 14C in living tissue is constant (about 15 disintegrations per
minute per gram of carbon. So after 5730 years there will be only 7
disintegrations per minute.)
When an organism dies, no more 14C is consumed.
The level of 14C decreases as the dead tissue ages.
The half-life for carbon-14 is 5730 years. This dating method works
well for objects up to 50,000 years old. (note: after about 4 half lives
carbon-14 is ineffective at dating things.)
32
Example:
Carbon-14 has a half-life of 5730 years and is used to date archaeological

objects.
All living organisms have a constant carbon-12/carbon-14 ratio. When the

organism dies carbon-12 levels remain constant but carbon-14 decays. The
changing carbon-12/carbon-14 ratio can be used to determine the date of the
artifact.
For example, fresh charcoal made from a tree contains carbon-14 which will give
a radioactive count of 13.60 disintegrations per minute per gram of carbon.
Prehistoric cave paintings were found in Spain. A piece of charcoal found in the
ancient cave in Altamira, Spain gave 1.70 disintegrations per minute per gram of
carbon. From this information, determine the age of the cave paintings. After one
half-life the number of disintegrations will go from 13.60 to 6.80; after two half-
lives it is 3.40 and after three half-lives 1.70. Therefore 3 half-lives have elapsed
since the paintings were done. Since the half-life of carbon-14 is 5730 years the
paintings are about 5730x3=17,190 years old.
33
Problem:
A wooden object from an Egyptian tomb is subjected to radiocarbon

dating. The decay rate observed for its carbon-14 content is 7.2 dis
min–1 per g carbon. What is the age of the wood in the object (and,
presumably, of the object itself)? The half-life of carbon-14 is 5730
years, and the decay rate for carbon-14 in living organisms is 15 dis
min–1 per g carbon.
Solution:
Problem:
The half-life of carbon-14 is 5730 years. A piece of linen found today

contains carbon-14 and gives an activity of 15 counts per minute per
gram of carbon. If an anthropologist found an ancient piece of linen
believed to date back to the Neolithic period which gave only 7.5
counts per minute per gram of carbon, how old is the ancient linen?
[5730 yrs]
34

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Physical Chemistry II – Thermodynamics Prepared by Chan Chin Han

Physical Chemistry II (CHM 520)

Lecture (3 hrs/week); Practical (3 hrs/week)

1. Assess concepts for thermodynamics, solutions of electrolytes,

2. Conduct scientific investigation in areas on thermodynamics,

3. Communicate in writing the scientific investigations.

Lab 1: Heat-capacity ratios for gases.

2.0 Solutions of electrolytes.

Lab 3: Faraday’s laws.

3.0 Electrochemical cells.

Lab 6: Electrochemistry and thermodynamics.

The First Law

• Thermodynamics are the study of the transformations of energy.

• The universe is divided into:

Work, heat and energy

Thermodynamics is concerned with energy changes that accompany

Energy of a system is its capacity to do work. (e.g. by winding a

When the energy of a system changes as a result of a temperature

A wall is diathermic if a change of state is observed when two objects

Endothermic process Exothermic process

In a diathermic container, In a diathermic container,

A wall is adiabatic if no change occurs even though the two objects

Endothermic process Exothermic process

In an adiabatic system, the In an adiabatic system, the

The First Law

Unit for U, w, q are joule (J).

In a closed system, the change in internal energy is equal to the

Note: the internal energy of an isolated system is constant.

Work and Heat

Expansion work – the work arising from a change in volume.

e.g. the work required to move an object a distance dz against an

External pressure, Pex

To achieve reversible expansion we set pex equal to p at each stage

Isothermal reversible expansion: (of a perfect gas)

Heat and Enthalpy

At constant volume, no additional work,

For measurable change,

The internal energy of a substance increases when its temperature is

For example, the sample may be a gas in a container of fixed volume.

Heat capacity at constant volume, Cv (J K-1)

In general, heat capacities depend on the temperature and decrease

If the heat capacity is independent of temperature over the range of

*Fig. 10 The internal energy of a system increases as the temperature is raised;

Fig. 12 When a system is subjected to constant pressure and is free

In this case, the heat supplied is equal to the change in another

A change in enthalpy is equal to the heat supplied at constant

For a measurable change,

If a process involves only solids or liquids, the values of ΔH and ΔU

the surroundings when the process occurs, so the energy supplied as

The enthalpy of a perfect gas:

This relation implies that the change of enthalpy in a reaction that

Δng is the change in the amount of gas molecules in the reaction.

e.g. 2H2 (g) + O2 (g) → 2H2O (l),

The variation of enthalpy with temperature

The enthalpy of a substance increases as its temperature is raised.

The most important condition is constant pressure, and the slope of

Heat capacity at constant pressure, Cp,

The heat capacity at constant pressure is used to relate the change in