Lecture Notes

Week 2
CHEM*2880 Physical Chemistry
Prof. Jennifer Murphy
Class Schedule – Part I
Week Dates Topics Text Ref Seminar

Week 0 Sept. 5 Introduction Review Chapter 1 First Class

Properties of Gases Ch 2, 2.1 – 2.3 Meeting

Properties of Gases Ch 2, 2.4 – 2.6 (p. 21) Properties of

Week 1 Sept. 8 – 12 & Spectroscopy Ch 14, 14.1 Gases Quiz #1
Ch 14, 14.2 – 14.4

Spectroscopy & 1st Ch 14, 14.5 – 14.8 Spectroscopy

Week 2 Sept. 15 – 19 Law of 14.9; Ch 3, 3.1 – 3.2 Quiz #2
Thermodynamics Ch 3, 3.3 – 3.4
1st & 2nd Law of Ch 3, 3.5 – 3.7 Thermodynamics
Week 3 Sept. 22 – 26 Thermodynamics Ch 4, 4.1 – 4.3 Quiz #3
Ch 4, 4.4 – 4.5
2nd Law of Review Test #1 (material
Week 4 Sept. 29 – Oct. 3 Thermodynamics & Ch 4, 4.6 – 4.9 up to Sept. 29
Solutions Ch 5, 5.1 – 5.2 lecture.)
Chapter 14 - Spectroscopy
14.1 Vocabulary
14.2 Microwave Spectroscopy
14.3 Infrared Spectroscopy
14.4 Electronic Spectroscopy
14.5 Nuclear Magnetic Resonance
14.6 Electron Spin Resonance
14.7 Fluorescence and Phosphorescence
14.8 Lasers
14.9 Optical Rotary Dispersion and Circular Dichroism
Nuclear Magnetic Resonance
Nuclear Magnetic Resonance (NMR) is a spectroscopic
method that is very powerful for a scientist.

Whereas IR gives information about functional groups, NMR

gives information about the number of each of the distinct
types of hydrogen nuclei as well an information regarding the
nature of the immediate environment of each type.

Commonly used with IR for structure determination.

Spin
 Just as electrons have spin (±1/2), nuclei also have spin states
which can take on both integer and half-integer values: I = 0, 1/2, 1,
3/2, 2…
 If a nucleus has a value of I = 0, this means it has no spin and is
not NMR active.
 Nuclei with spin can adopt 2I + 1 spin orientations which are
degenerate (same energy) in the absence of magnetic field. In the
presence of an external magnetic field, they have different energy.
 Many common nuclei such as 1H, 13C, 15N and 31P have spin states
of ½ which means in a magnetic field, they have 2(1/2) + 1 = 2 spin
orientations. These orientations are called magnetic moments, mI
and will take on values of +1/2 and -1/2.
Energy of Spin State
The energy of a spin state is given by EI
which is directly proportional to both
mI and the strength of the magnetic
field, Bo, and the gyromagnetic ratio, γ,
which is a constant for the nucleus
being studied.

ΔE between spin states is very small,

and so the spin states are nearly Difference in energy between nuclear
equally populated, but the distance spin levels in an external magnetic
field
can be increased by increasing the
magnetic field strength.
Practice Problem
Calculate the magnetic field, Bo, that corresponds to a
precession frequency of 400 MHz for 1H.
Isotopic Abundance
Isotope abundance and specific properties of the nucleus (i.e.,
the nuclear gyromagnetic ratio (𝛾𝛾) that directly affects the
size of the magnetic moment) determine the spectral
sensitivity of a nucleus.
Chemical Shifts
 NMR is useful because a nucleus is very sensitive to its chemical
environment. Different protons have different resonance frequencies
due to local environmental effects experienced by a nucleus.
 The frequency of a NMR peak is expressed relative to a reference
frequency – a compound with protons that resonate at a high
frequency extreme, e.g., tetramethylsilane (TMS) for organic systems.
 The chemical shift, 𝛿𝛿, is defined as the frequency difference between
the reference peak (𝜐𝜐0) and the observed peak (𝜐𝜐) so that it is
independent of the magnitude of the applied field, i.e.,
𝜐𝜐 − 𝜐𝜐0
𝛿𝛿 = x 106
𝜐𝜐𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
 𝛿𝛿 is a unitless number, however normally expressed in terms of parts
per million (ppm)
Shielding
 The local magnetic moments of nuclei in a molecule are affected
by its electron cloud. Local environments can affect the density of
the electron cloud and change the frequency at which it
precesses.
 If a nucleus has a greater electron density, it elicits a larger
opposing magnetic field and will appear at a low chemical shift.
Nuclei with greater electron density are considered to be
“shielded”.
 If the nucleus is in an electron withdrawing environment, this will
reduce the electron density, decreasing the opposing magnetic
field, and will appear at high chemical shift. Nuclei with less
electron density are considered to be “deshielded”.
Shielding
An example of an electron withdrawing environment is nearby an
electronegative nucleus (e.g., halogen), or when resonance effects can
pull electron density away from the nucleus (e.g., ketones, aldehydes,
carboxylic acids, aromatics).

Low shielding Higher shielding

High frequency Low frequency
Chemical Shifts
Chemical Equivalence
Two or more nuclei are chemically
equivalent if they are related by a
symmetry operation. They will have
the same chemical shift.

Each of these molecules has some

chemically equivalent 1H nuclei:
Integration
The integrated area under 1H NMR peaks is directly
proportional to the number of protons giving rise to that
signal. You can often assign simple NMR spectra based entirely
on integration.

Integration values will always be given on a test or exam.

Spin-Spin Coupling
 Nuclei can interact through their bonds in a process known as
spin-spin coupling or J coupling. This is typically observed for
nuclei separated by no more than three bonds.

 This coupling results in a splitting of peaks into a number which is

determined by the binomial distribution.

 Equivalent protons will not split each other because they are in
the same chemical environment.

 The frequency separation between split lines is the spin-spin

splitting and is given by J in Hz (independent of the magnetic
field).
Spin-Spin Coupling
It’s common for signals of different H atoms to split into close groupings
of two or more resonances.
Common patterns are doublets (2 equal intensity signals), triplets (3
signals; intensity ratio of [Link]) and quartets (4 signals; intensities of
[Link]).

Pattern predicted by “n+1 rule”

(n = neighboring nuclei)
e.g., for a doublet: n = 1; n+1 = 2
a quartet: n=3; n+1 = 4
Spin-Spin Coupling
Splitting Example CH3CH2OH
Pascal’s Triangle

Spin-spin splitting b/w CH2

and CH3 groups in ethanol.
Ethanol Peak Assignment
H2
C CH3 protons assigned based on:
H 3C OH
 Peak integrating to 3

 Low chemical shift

 Split by 2 neighboring protons into a triplet

CH2 protons assigned based on:

 Peak integrating to 2

 Split by 3 neighboring protons into a quartet (OH

protons often don’t contribute to splitting)

OH proton assigned to remaining peak integrating

to 1, at a higher chemical shift
1-Propanol
For the sake of this course, we will say that the proton on an
OH is not split and does not take part in the splitting.
Practice Problem 2-phenethyl propionate
The 1H NMR spectrum of 2-phenethyl propionate is shown below. Assign
the peaks in the spectrum.
d b
H H2 H2
C C O C
HC e C C CH3
H2 a
HC CH c O
C
H
Practice Problem Match the Spectrum
Match the
molecules to their
correct 1H NMR
spectrum.
A.

B.
Degree of Unsaturation (Ω)
 A calculation of the degree of unsaturation (Ω) is a good
way to start a spectroscopy problem. It tells you how many
rings and double bonds are in the molecule; thus, you know if
you should look for a carbonyl or a carbon- carbon double
bond, or a ring or an aromatic ring.
 can be determined from the molecular formula
Rule 1: Replace all halogens in formula by H’s.
Rule 2: Omit oxygens and sulfurs.
Rule 3: For each N, omit N and subtract one H.
End up with CnHm and use
Ω=
( 2n + 2 ) − m m
= n − +1
2 2
Degree of Unsaturation Example Calculation
 can be determined from the molecular formula
Rule 1: Replace all halogens in formula by H’s.
Rule 2: Omit oxygens and sulfurs.
Rule 3: For each N, omit N and subtract one H.
End up with CnHm and use ( 2n + 2 ) − m m
Ω= = n− +1
Example: C8H8NOBr 2 2
Apply rule 1: C8H9NO This means that the
molecule has 5 rings and/or
Apply rule 2: C8H9N pi bonds (or any
Apply rule 3: C8H8 combination of the two).

Ω= 8 – 4 + 1 = 5 likely to be an A Ω ≥ 4 doesn’t demand but

aromatic (benzene) ring should suggest the
possibility of an aromatic
(benzene) ring.
 Ex. 6: C6H15N

Ω = 6 – 14/2 + 1 = 0

IR peaks (cm-1): N-H str.

3384
2988, 2934 & 2870
1170

C-H str. C-N

str.

Answer: Diisopropylamine

n+1=7 n+1=2

25
Fluorescence and Phosphorescence
The phenomenon of fluorescence and phosphorescence can be
represented by a Jablonski diagram:
There a singlet ground (S0), and excited first (S1)
S1 internal conversion electronic state where fluorophores can exist in
intersystem crossing
different vibrational levels (0, 1, 2, etc.). After light
absorption, a fluorophore is usually excited to a
higher vibrational level (S1 or S2) and then rapidly
T1 relaxes to the lowest vibrational level of S1, this is
referred to as internal conversion.

The return to the ground state (S0) then results

in the emission of fluorescence. Molecules in the
S1 state can also undergo spin conversion to the
first triplet state T1 (intersystem crossing). The
S0 emission from the T1 state is called
phosphorescence and generally has longer
wavelengths (lower energy) compared to
fluorescence.
Fluorescence
Fluorescence is the emission of light from an excited
electronic state.
 Molecules absorb light, moving them higher electronic
state.
 Frank-Condon Principle states that transition to
excited state is vertical, i.e., nuclei do not change their
positions during an electronic transition.
 Excited molecules rapidly lose some excited
vibrational energy non-radiatively (light not given off,
but instead heat is released) and return to the lowest
vibrational state within the excited electronic level; this
is called internal conversion.
 Once in the ground vibrational state of the excited
electronic level, the molecule emits light as Relation between absorption and
fluorescence; emitted light is at a lower frequency fluorescence.
(longer 𝝀𝝀) than original transition.
Fluorescence
The intensity of radiation emitted after the exciting light is turned off (I) is defined by:
𝐼𝐼 = 𝐼𝐼0 𝑒𝑒 −𝑡𝑡/𝜏𝜏

where I0 = is the intensity at t=0 and 𝜏𝜏 is the mean lifetime of the fluorescence state.

 Fluorescence follows first-order kinetics and the rate constant (k) for the decay
is given by 1/𝝉𝝉
 Fluorescence spectra and maxima of emission are often very sensitive to the type of
environment, and fluorescence spectra can be used to probe molecular
environments.
 changes in shape or position of fluorescence spectrum reflects environment in
which the fluorescing molecules (fluorophore) exists.
 can measure excitation spectrum, i.e., fluorescence intensity measured as 𝜆𝜆 of
excitation light varied; fluorescence intensity changes proportionally to amount of
absorption.
Fluorescence
Fluorescence has become the most widely used spectroscopy
in biology as many biological substances emit a characteristic
fluorescence such as:
 Chlorophyll (red fluorescence)
 Jellyfish (green fluorescence)
 Many proteins (fluoresce from
tryptophan residues)
Jellyfish with Green Fluorescent Protein (GFP)

Image from: Protein databank, Green

Fluorescent Protein (GFP)
Phosphorescence
Phosphorescence is also the emission of light from
an excited electronic state, although from a different
path than fluorescence.
 Phosphorescence cannot be studied in the liquid
state because the excited triplet state can be
easily deactivated through collisions.
 Emission pathway involves a change in spin state
from an excited singlet state to an excited triplet
Some algae have the ability to phosphoresce, and the resulting
state (i.e., the phosphorescent state is light is known as “bioluminescence”.

paramagnetic and has 2 unpaired electrons)

through a process known as radiationless transition. Phosphorescent spin state transitions
are “forbidden” and therefore have a low
probability and a longer lifetime than
 Return to the ground singlet state from the excited
fluorescent emissions.
triplet state produces phosphorescence.
Fluorescence and Phosphorescence
Two characteristics distinguish the two:
1) phosphorescence has a much longer decay period than
fluorescence (several versus 10-3 seconds).
2) a molecule in the phosphorescent state containing two
unpaired electrons, i.e., triplet state
What makes compounds fluoresce?
 Many compounds just release absorbed energy in the form of
heat instead of light.
 Fluorescence depends on a # of factors, e.g., electron orbitals, ΔE
between ground & excited states, etc.
 Compounds that fluoresce have:
 conjugated p system (circled in blue) , and
 at least one electron donating group (circled in red).
Example: Quinine
Practice Problem Worked Example
The luminescent 1st-order decay of a certain organic molecule yields
the following data where I is the relative intensity.

t/sec 0 1 2 3 4 5 10
I 100 43.5 18.9 8.2 3.6 1.6 0.02
Calculate the mean lifetime, τ, for the process. Is this fluorescence or
phosphorescence?
where I0 = intensity @ t = 0 and τ is the mean lifetime of the
fluorescence state.
We see at t = 0, I0 = 100.
To produce a linear plot, divide by I0 and take the natural log, i.e.,
 I  1
ln   = − t
 I0  τ
 Time (seconds)
0
0 1 2 3 4 5 6 7 8 9 10
-1

-2

ln (I/I0)
-3

-4

-5

-6

-7 y = -0.8506x + 0.0413
-8
R² = 0.9997
-9

slope =-0.8506 = -1/τ

∴ τ = 1.18 seconds
This is a long lifetime, corresponding to phosphorescence.

34
Optical Rotary Dispersion and Circular Dichroism
 optically active molecules (chiral) rotate plane-polarized light.
 If pure sample containing 1 enantiomer, emerging light beam has a different
plane of polarization than entering beam:
 dextrorotatory (+): plane is rotated clockwise, or CH2OH
 levorotatory, ( – ): plane is rotated counter-clockwise. H C* Cl

 If 50:50 mix of enantiomers, no rotation observed. CH3

 rotation depends upon λ, path length, concentration, T, solvent, etc.

𝛼𝛼
 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝛼𝛼 𝜆𝜆 (deg·cm ·dm ·g )=
𝑇𝑇 3 -1 -1
𝑙𝑙𝑙𝑙
 (measured at a particular T, conc’n (g/mL) & λ, normally 589 nm, the Na “D line”)

𝛼𝛼 𝑇𝑇
𝜆𝜆 ×𝑀𝑀𝑀𝑀
𝜆𝜆 (deg·cm ·dm ·mol )=
𝑇𝑇
 𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝛷𝛷 3 -1 -1
100
Practice Problem
Calculate the observed rotation of a solution of 0.5245g of (S)-1-amino-
1-phenylethane diluted to a volume of 10.0 mL with methanol at 20°C,
using the D line of a sodium lamp and a 1.00 dm tube. Specific rotation of
this material: [𝛼𝛼]23
𝐷𝐷=-30.0°. What is the molar rotation? CH3
Given: (S)-1-amino-1-phenylethane (MM: 121.18 g/mol) C* H
NH2
Practice Problem
The specific rotation of a pure substance is -5.90 degrees. What
is the percentage of this isomer in a mixture with an observed
specific rotation of -2.95 degrees?
Chapter 3 – First Law of Thermodynamics
3.1 Work and Heat
3.2 The First Law of Thermodyanmics
3.3 Heat Capacities
3.4 Gas Expansion
3.5 Calorimetry
3.6 Thermochemistry
3.7 Bond Energies and Bond Enthalpies
What is Thermodynamics
The science of heat and temperature, and of the laws governing the conversion
of thermal energy into mechanical, electrical, or other forms of energy.
Thermodynamics is a macroscopic science (i.e., is based on the properties of
the system and not the individual molecules or atoms – although they can give
us thermodynamic information via statistics)
Thermodynamics can tell us:
1. The maximum efficiency with which we can transform one energy into
another
[Link] preferred direction of a reaction or conversion
3. Relationships between energy forms
4. Equilibrium and equilibrium concentrations
it cannot tell us about reaction rates (this is kinetics)
Thermodynamic System
Thermodynamic System
The substance under study in which a change occurs is
called the thermodynamic system (or just system). i.e., the
part of the universe we are studying

Thermodynamic Surroundings
Everything else in the vicinity is called the
thermodynamic surroundings (or just the
surroundings). i.e., the rest of the universe.
Surroundings are assumed infinite and remain at constant
temperature and pressure.
The boundary:
• may be actual (test tube) or theoretical (a galaxy)
• controls transfer of work, heat and matter from the
system to the surroundings and vice-versa.
Open, Closed, and Isolated Systems
An open system may exchange
both energy and matter w/ its
surroundings.
A closed system may exchange
energy but not matter w/ its
surroundings.
An isolated system may exchange
neither energy nor matter w/ its (a) open system; (b) closed system; and
surroundings (c) isolated system
Diathermic and Adiabatic
A diathermic system allows heat flow into or out of the
system.
An adiabatic system prevents heat flow into or out of the
system. q=0.
Diathermic and Adiabatic Walls
Both containers are attempts to
create adiabatic walls.

The thermos is a good approximation

to an adiabatic calorimeter – the cup
is not…
State Functions and Process Functions
State Function Process Function

An equation that describes properties of the

An equation that describes
system that depends only on the current state of
properties of the system that
the system, and not the way in which the system
depend on the specific path
acquired that state (e.g., the system is at 25°C, but
between two states.
we don’t care if it was hotter or colder to start).
Examples of process function
Properties in the state function equation are known
properties include mechanical
as state variables or state quantities (e.g., mass,
work, heat, and time.
pressure, temperature, volume, enthalpy, Gibbs
These are pathway dependent
energy).
properties
State functions can be intensive or extensive.
Intensive and Extensive Properties
We aim to describe the state of
the system by understanding Intensive Extensive
experimental variables and Properties Properties
properties such as: Properties which are Properties which are
 Pressure not dependent on the directly proportional to
amount of material the amount of material
 Volume present in the system present in a system

 Temperature • Temperature • Volume

• Density • Mass
 Composition • Pressure • Area
• Electrical potential • Energy
• Electrical charge

 Properties can be either

intensive or extensive.

45
State Functions
A state function describes state of system.
The following are all state functions:
 Pressure, P
 Volume, V
 Temperature, T
 Mass, m
 Quantity, n
 Internal Energy, U
 Enthalpy, H
 Entropy, S
 Gibbs Energy, G
Energy Transfer
Systems will transfer different forms of energy in and out. This
energy can come in the form of either work (w) or heat (q).
The overall internal energy of a system is denoted U.
1st Law of Thermodynamics: Energy cannot be created or
destroyed, only transferred in and out of a system.
Therefore, the change in internal energy for a system U1 to U2 is
equal to the sum of work and heat in a closed system.
Restricted Pathways

Image from: Thermodynamic Processes: Isobaric, Isochoric, Isothermal and Adiabatic processes, YouTube Video:
[Link]
Reversibility
A reversible process is a theoretical
concept which states that a system is
always infinitesimally close to equilibrium.

This would be the pathway of maximum

efficiency with respect to energy transfer.
Irreversible Process. If the
system were truly reversible, we All real-world processes are irreversible .
would be able to regain the A reversible process would take an infinite
initial state of T1, p1 and V1, but
we will lose some energy as heat amount of time to complete
to the surroundings and the final
state will be T3, p1, V3. Image
from: Wikipedia: Irreversible
Process.
 Work
An energy transfer between the system and
the surroundings that is not heat. e.g., the
system lifting or lowering a weight in the
surroundings.
Work done by the surroundings on a system
is positive (lowering of the weight in the
surroundings).
Commonly discussed as an increase or
decrease in volume (expansion or
compression of a gas).
This expression gives the amount of work
performed by a gas during expansion from V1
to V2 at constant T, with Pex as the external,
opposing pressure.
Isothermal expansion of a gas (Pex is simulated by
placing a mass on the top of the “piston”)
Gas Expansion
For a gas to expand, Pin has to be We can calculate the work being done by an
greater than Pex, and as a gas isothermal system moving from the state of P1V1 to
expands against an external
P2V2 via gas expansion using one of two methods:
pressure, the internal pressure
decreases. 1) Decrease P1 to P2 then V1 to V2
The piston will come to a halt, and 2) Infinitesimally small stages pressure and volume
the work will end when Pin = Pex.
change (i.e., integration over the pathway of V1
Work is not a state function and is to V2 by the change in volume, dV)
dependent on the path taken.
Isothermal gas expansion from P1V1 to P2V2. a)
an irreversible process. Note that P2 is equal
to the constant external pressure.
b) a reversible process. In each case the
shaded area represents the work done during
expansion. More work is done during a
reversible process.
Gas Expansion

Reversible Isothermal Expansion

This is an approximation of reality based on a reversible
process that allows us to calculate the efficiency of a
real process of gas expansion in a system.
Heat and Work Conventions
 Path functions are positive when energy enters the system.
 Path functions are negative when energy leaves the system.
 They are often defined as:
heat supplied to the system, qin
mechanical work done on the system, won
Work, w Heat, q
+ve when work is done on the +ve when a system absorbs heat,
system, energy is added energy is added
-ve when the system does work on -ve when a system evolves heat,
the surroundings, energy is energy is subtracted
subtracted
Practice Problem (3.1 Textbook)
A quantity of 0.850 mole of an ideal gas initially at a pressure
of 15.0 atm and 300 K is allowed to expand isothermally until
its final pressure is 1.00 atm.
Calculate the value of the work done if the expansion is
carried out:
(a) against a vacuum
(b) against a constant external P = 1.00 atm
(c) reversibly
Practice Problem (3.1 Textbook)
Heat
The energy that flows into or out of a system because of a difference in
temperature between the thermodynamic system and its surroundings.
 We refer to energy transfers in the form of heat as heat flow, heat
absorbed, and heat released.
 Like work, heat is a path function (i.e., it is dependent on the pathway
taken).
 Energy flows from the direction of higher temperature to lower
temperature. Once two bodies are in thermal equilibrium, the term heat
no longer applies (Zeroth Law of Thermodynamics).

More detail on these equations soon!

Definitions of Heat Capacity
Heat Capacity, C, is the heat energy required to raise an object’s
temperature by 1 Celsius degree or 1 Kelvin unit, i.e., C = q/∆T; Units:
Joules/degree
Heat capacity is an extensive property

Specific Heat Capacity, C s or s= C/m Units: J·K-1·kg-1

Molar Heat Capacity, C m = C/n Units: J·K-1·mol-1

Specific Heat Capacity and Molar Heat Capacity are intensive properties.
Heat Capacity
Heat Capacity, C, of a Sample of Substance
The quantity of heat needed to raise the temperature of the sample of
substance by one degree Celsius (or one Kelvin).
Molar Heat Capacity
The heat capacity for one mole of substance. The amount of heat
needed to raise 1 mole through 1 °C or 1 K unit (or the heat capacity per
mole). Units: J∙K–1∙mol–1
Specific Heat Capacity, C s or s (or specific heat)
The quantity of heat needed to raise the temperature of one gram of
substance by one degree Celsius (or one Kelvin) at constant pressure.
Units: J∙g–1∙K–1 e.g., H2O(l) Specific Heat = 4.184 J∙g–1∙deg–1
Heat Capacity
The heat required can be found by using the following equations.

Using heat capacity:

q = CΔT
Where C is the heat capacity with units J∙K–1

Using molar heat capacity:

q = n x Cm x Δ T
Where Cm is the molar heat capacity with units J∙K–1∙mol–1

Using specific heat capacity:

q = cs x m x Δ T
Where cs or s is the specific heat capacity with units J∙g–1∙K–1
Specific Heat Capacities (J·K ·kg )
-1 -1

Specific Heat Capacity for H2O = 4184 J·K-1·kg-1

OR 4.184 J ·K-1·g-1
Isochoric & Isobaric Heat Capacities
Isochoric heat capacity: 𝜕𝜕𝜕
Cv = qv/∆T = ∆U/∆T; Cv =
𝜕𝜕𝜕 v
Isobaric heat capacity:
Cp = qp/∆T = ∆H/∆T; 𝜕𝜕𝜕
Cp =
𝜕𝜕𝜕 p

C tends to increase with

increasing T, but if ∆T is
small (≤ 50 K) we can
treat Cp and Cv as if
they are constant.
CP,m & CV,m Relationship for an Ideal Gas
Hm = Um + RT
For a change in temperature, ∆T
∆Hm = ∆Um + R∆T Δ𝐻𝐻𝑚𝑚 Δ𝑈𝑈𝑚𝑚
= + 𝑅𝑅
Δ𝑇𝑇 Δ𝑇𝑇

After substitutions:
1
CP,m = CV,m + R where R = 8.314 J·K-1·mol-
5
Monoatomic ideal gases: 𝐶𝐶̄𝑝𝑝 = 𝐶𝐶̄𝑣𝑣 + 𝑅𝑅 = 𝑅𝑅
2
Practice Problem (3.3 Textbook)
Calculate the values of ∆U & ∆H for the heating of 55.40 g of Xe from 300 K
to 400 K. Assume ideal-gas behaviour and heat capacities at constant
volume and constant pressure are independent of T.
Physical Changes - Gases
I. Isothermal expansion (or compression) of a perfect gas,
i.e., constant T; ∆T = 0.
II. Reversible compression (or expansion)
at constant P (isobaric; ∆P = 0)
III. Reversible pressure change at constant volume (i.e.,
isochoric)
IV. Adiabatic expansion (no heat enters or leaves system, i.e.,
perfectly insulated)
I. Isothermal expansion (or compression) of a perfect gas,
i.e. , constant T; 𝚫𝚫T = 0.
e.g., a system is placed in a water bath; heat leaves or enters
system to keep T constant,
i.e., ∆U = 0 and ∆H = ∆U + nR∆T = 0
For a reversible path where P = Pex

Δ𝑈𝑈 = 0 = 𝑞𝑞 + 𝑤𝑤 ∴ 𝑞𝑞 = −𝑤𝑤 P1, V1, T1

𝑉𝑉2 𝑃𝑃1 P2, V2, T1
𝑤𝑤𝑇𝑇 = −𝑛𝑛𝑛𝑛𝑛𝑛 ln = −𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1 𝑃𝑃2
𝑉𝑉2 𝑃𝑃1
𝑞𝑞𝑇𝑇 = −𝑤𝑤𝑇𝑇 = 𝑛𝑛𝑛𝑛𝑛𝑛 ln = 𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1 𝑃𝑃2
II. Reversible compression (or expansion) at constant P
(isobaric; 𝚫𝚫P = 0)
∆T ≠ 0; could do this by lowering T of surroundings,
i.e., take heat away from system
At constant P: qp = ∆H and ∆U = q + w = ∆H – P∆V.
nRT2 nRT1
wP = −Pex ΔV = −P V2 − V1 = −P1 −
P1 P1
wP = −nR(T2 − T1 ) = −nRΔT
T1 > T2
qP = ΔH = Cp (T2 − T1 ) = nC̄ p ΔT
A
P1, V1, T1
Since ∆U = q + w B
∆U = Cp(T2 – T1) − nR(T2 – T1) P1, V2, T2

∆U = (Cp – nR)∆T = Cv ∆T
III. Reversible pressure change at constant volume (i.e. ,
isochoric)
P1, V1, T1
e.g., a bomb calorimeter
A
T 1 > T2
where ∆V = 0 and w = 0
C
∴ Δ𝑈𝑈𝑉𝑉 = 𝑞𝑞𝑉𝑉 = 𝐶𝐶v Δ𝑇𝑇 = 𝑛𝑛𝐶𝐶̄v Δ𝑇𝑇 P2, V1, T2
Δ𝐻𝐻 = Δ𝑈𝑈 + Δ(𝑃𝑃𝑃𝑃) = Δ𝑈𝑈 + 𝑛𝑛𝑛𝑛𝑛𝑛𝑛
Δ𝐻𝐻 = 𝐶𝐶v Δ𝑇𝑇 + 𝑛𝑛𝑛𝑛𝑛𝑛𝑛 = (𝐶𝐶v + 𝑛𝑛𝑛𝑛)Δ𝑇𝑇 = 𝐶𝐶𝑝𝑝 Δ𝑇𝑇

Note: In reversible isobaric and isochoric processes, the work and heat values
are different, but 𝚫𝚫U and 𝚫𝚫H are identical. That is, U and H are the same at point
B in ii) and point C in iii). This is because they are in the same isotherm (T2) and
for an ideal gas U and H depend only on T and remain constant as T remains
constant. We know this from process i).
IV. Adiabatic expansion (no heat enters or leaves system,
i.e., perfectly insulated)

q = 0 but ∆T ≠ 0 and ∆U = w
 For an ideal gas, U depends only on T, i.e.,
𝑤𝑤 = Δ𝑈𝑈 = 𝐶𝐶v Δ𝑇𝑇 = 𝑛𝑛𝐶𝐶̄v Δ𝑇𝑇
 Since work is done by the system during an expansion, the
internal energy decreases and T drops, e.g., T 1 > T2
 letting air out of a bicycle tire
A
 T increases during compression P1, V1, T1
D
 In this case, P, V and T are all changing
P2, V2, T2
Without going into the derivation, it can be shown
ϒ−1 ϒ
𝑇𝑇2 𝑉𝑉1 𝑃𝑃2 𝑉𝑉1
= 𝑎𝑎𝑎𝑎𝑎𝑎 = or P1 𝑉𝑉1ϒ = P2 𝑉𝑉2ϒ
𝑇𝑇1 𝑉𝑉2 𝑃𝑃1 𝑉𝑉2
𝐶𝐶𝑝𝑝
where ϒ =
𝐶𝐶𝑣𝑣
i.e., adiabatic expansions PVϒ = constant
Remember for a monoatomic ideal gas:
3 5 Cp 5
𝐶𝐶𝑣𝑣 = 𝑛𝑛𝑛𝑛 and 𝐶𝐶𝑝𝑝 = 𝑛𝑛𝑛𝑛, γ =
∴=
2 2 Cv 3
Work (hatched area in previous slide) is less than for isothermal
expansion.
As before, Δ𝐻𝐻 = Δ𝑈𝑈 + Δ 𝑃𝑃𝑃𝑃 = Δ𝑈𝑈 + 𝑛𝑛𝑛𝑛𝑛𝑛𝑛
Δ𝐻𝐻 = 𝐶𝐶v Δ𝑇𝑇 + 𝑛𝑛𝑛𝑛𝑛𝑛𝑛 = (𝐶𝐶v + 𝑛𝑛𝑛𝑛)Δ𝑇𝑇 = 𝐶𝐶𝑝𝑝 Δ𝑇𝑇
Practice Problem
A quantity of 0.850 moles of a monatomic ideal gas initially at a pressure
of 15.0 atm and 300 K is allowed to expand until its final pressure is 1.00
atm. Calculate the work done if the expansion is carried out adiabatically
and reversibly.
Practice Problem (3.81 Textbook)
Indicate whether the following thermodynamic quantities are positive,
zero, or negative for the system described. Clearly state your reasoning
for each answer.
i. heating of a gas at constant volume
w
q
ΔH
ΔU

ii. irreversible isothermal expansion (ideal gas)

w
q
ΔH
ΔU
Physical Changes – Liquids and Solids
Isobaric (i.e., ∆P = 0)
 Heating a solid or liquid at constant P can be handled by:
qP = C p ∆T = nC p ∆T
 For work at constant P, ΔV ≈ 0: wP =− Pex ∆V ≅ 0
∴∆U = q + w = nCP ∆T
∴∆H = ∆U + ∆( PV ) =∆U + P∆V ≅ ∆U
Isochoric (i.e., ∆V = 0) q = C ∆T = nC ∆T
V v v

w=− Pex ∆V =0
∆U = q + w = Cv ∆T
∆H = ∆U + ∆( PV ) ≅ ∆U
Physical Changes – Liquids and Solids
Isothermal (i.e., ΔT = 0)
 Changing pressure leads to negligible volume changes (in
most cases) at constant T
qT ≅ 0
∆U =+ 0 ∆H
q w ==
wT ≅ 0
For changes of state for a pure solid or liquid, use a convenient
path to find q & w values, and sum to get ΔU.
e.g., isobaric path + isothermal path
isochoric path + isothermal path
For solids & liquids, since V doesn’t change appreciably with P:
CP ≅ CV , ΔUP ≅ ΔUV and ΔH = ΔU
Phase Transitions
A change of state or phase transition is a change of a substance from
one state (solid, liquid, gas) to another. The specific name or names for
each of these transitions are given below. Remember, temperature is
constant during a phase change!
Practice Problem
Compare the difference between ∆H & ∆U for the following:
(a) 1 mol ice → 1 mol water at 273K & 1 atm
(b) 1 mol water → 1 mol steam at 373 K & 1 atm
Given: Vm (L/mol) @ 273 K Vm (L/mol) @ 373 K
Ice: 0.0196
Water: 0.0180 0.0188
Steam 30.61
Practice Problem Solution
Practice Problem (3.79 Textbook)
State the conditions for each of the following:
(a) ∆H = ∆U + P∆V (b) Cp = CV + nR (c) γ = 5/3
Heating Curve for Water
q = mCs(steam)∆T

boiling point qp = n∆H°vap gas

100°C

Temp q = mCs(liquid)∆T
(°C)
liquid
qp = n∆H°fus (kJ/mol)
= m∆H°fus (kJ/g)
0°C melting point
solid q = mCs(ice)∆T = n𝐂𝐂�(ice)∆T
Time heat supplied
Enthalpy (ΔH) Changes
For a chemical reaction: nAA + nBB → nCC + nDD

∆H
= ∑H products − ∑ H reagents
∆H
= nC H C + nD H D − nA H A − nB H B
Using standard enthalpy of formation values:
ΔH°Rxn = ΣnΔHf° (products) – ΣnΔHf° (reagents)

Can also use Hess’ Law to determine ΔH°Rxn values.

Refer to Metabolism of Glycine Example in Prof. Jones Notes
Dependence of ΔH on T
If ΔH or ΔU are known at one temperature, and need to be calculated at another, an
appropriate paths can be chosen.
Follow the path:
1 H2O (l) (35°C, 1 atm) → H2O (l) (100°C, 1 atm) (isobaric )
2 H2O (l) (100°C, 1 atm) → H2O (g) (100°C, 1 atm)
3 H2O (g) (100°C, 1 atm) → H2O (g) (35°C, 1 atm) (isobaric)
H2O (l) (35°C, 1 atm) → H2O (g) (35°C, 1 atm)

Step 1 is an isobaric heating of liquid water: ΔH1 = qP = CP(l)ΔT1

Step 2 is the vaporization of water at 100°C which we can look up in our standard
tables
Step 3 is the isobaric cooling of water vapour: ΔH2 = qP = CP(g)ΔT2
Note that ΔT2 = -ΔT1
Thus, for the overall reaction
ΔH(35°C) = ΔHvap(100°C) + CP(l)ΔT1 + CP(g)ΔT2 (Use: ΔT2 = -ΔT1)
= ΔHvap(100°C) + CP(l)ΔT1 – CP(g))ΔT1
Dependence of ΔH on T
Kirchoffs Law
∆H(T2) – ∆H(T1) = [CP(products) – CP(reactants)][T2 – T1]
OR
∆H(T2) = ∆H(T1) + ∆CP∆T

This equation does not apply only to phase changes. It can be

used to determine the enthalpy change for any reaction at
another temperature. It does assume that the heat capacities
are constant over the range of T.
Practice Problem
25℃,1 𝑎𝑎𝑎𝑎𝑎𝑎
Question: Fe2O3(s) + 3H2(g) 2Fe(s) + 3H2O(l)
What is the enthalpy change at 358K?
Practice Problem
Bond Enthalpy
∆HB or BDE, is the energy required to dissociate the bond into
its constituent atoms or free radicals (species must be in the
gas phase)
e.g., H–H(g) → H•(g) + H•(g); ∆HB = +436 kJ/mol
Note: ∆HB = +436 kJ/mol ≅ 2 ∆H°f (H(g))

Tabulated bond enthalpies are averages.

ALWAYS a positive quantity

∴ΔHrxn° = ∑ BE(broken) – ∑ BE(formed)

Practice Problem
Let n = 0.10 moles, ideal monatomic gas
P1 = 4.0 bar; V1 = 0.50 L; T1 = 241.15 K
P2 = 2.0 bar; V2 = 1.00 L; T2 = 152.15 K
T3 = 481.70 K
Find q, w & ΔU for path B.
Practice Problem Path B