CHEM103 Thermo Lectures 2024 Carolyn Dillon

Texas City docks,
Galveston
16th April, 1947
Texas fertiliser plant,

17th April, 2013
Thermodynamics
Part 1
Dr Carolyn Dillon
Consultation:
Tues 10.30am -12.30pm
Email: carolynd@uow.edu.au
Room: 18.129
Structure of course
• Fundamentals
• Atoms ions and molecules – electrons Wks 2-5
holding it all together – atomic scale ideas
• Gases, liquids, solids – macro scale
related to the atomic scale Wks 6-7
• Reactions:
thermochemistry Wk 8
– How hot
– How likely thermodynamics Wk
– How far 9/10
equilibrium
– How fast
kinetics
What makes an explosive?
Building demolition,
Boston
1
What is Thermochemistry?
• Branch of Thermodynamics
Heat Work
ENERGY
Thermochemistry
Key chemical concepts:
• What are energy, heat and work?
• Energy level diagrams
• What is heat capacity
• How can we calculate the work, heat and U (Eint)
of an expanding gas?
• What is Enthalpy, and how do we determine it?
• What are the common “Heats of reactions”?
• How can we use bond energies to determine
enthalpy change
• Hess’s Law, for calculating reaction enthalpies
• Born-Haber cycle and Lattice Energies
What is Thermochemistry?
• Thermodynamics is the science of heat and
work and transformations of one to the other.
• Energy is the capacity to produce heat.
• Energy is also the capacity to do work.
• There are 2 kinds of energy:
– Kinetic energy:
– Potential energy:
• Thermochemistry is the branch of
thermodynamics that examines the heat
involved in chemical reactions.
2
Energy: The Joule
James Prescott Joule –

English physicist and
brewer!
1 J = 1 kg.m2.s-2
1818-1889
Energy Units = Joule
1 J = 1 kg.m2.s-2
“Calories” vs. calories

1 calorie = 4.184 J
= energy to heat 1 g of H2O by 1°C
1 “Calorie” = 1 kilocalorie = 1000 calories
3
Types of energy
Potential (Ep)
Ep
Kinetic (Ek)
Etot = Ek + Ep
Types of energy (molecular)

Potential Energy
Kinetic Energy
(heat, q)
Thermochemistry
• What are energy, heat and work, state functions?
enthalpy change
• Born-Haber cycles and Lattice Energies
4
State Function
• We have no way of knowing the “absolute” internal
energy of a system.
• This would be too difficult to measure.
• We DO know that the internal energy is
independent of the path by which it was achieved.
Chemical reactions and energy

So a substance in any state has potential and kinetic energy…
Let’s examine what changes during a chemical reaction…
e.g. Simple dissociation reaction:
(important reaction in photochemical smog)
N2O4 (g) + heat  2 NO2 (g)

Internal Energy (U)
2 NO2
heat
N 2O4
N2O4 (g) + heat  2 NO2 (g)
5
Internal Energy, U
heat 2 NO2
N 2O4
What kind of U have we changed?
• nuclear?
• atomic?
• vibration?
• bond?

e.g. More complex reaction
(transfer reaction, important in ozone depletion)
O3 + NO  O2 + NO2 + heat
U
O3 + NO
heat
O2 + NO2
O3 + NO  O2 + NO2 + heat
N2O4 + heat  2 NO2
6
U
products
heat
reactants
U
Endothermic reactants
U > 0 heat products
Exothermic
U < 0

Note: difference in Eint = heat
Internal Energy = U = q
These expressions have the same meaning.
Simple version of
“First Law of Thermodynamics”
Therefore - measuring heat  U (calorimetry)

- tabulating U  estimating heat
Systems and Surroundings

What is a System?
• The region where the reaction is taking place
What are the Surroundings?

• The region outside the system,
ie. A water bath that the reaction
vessel is sitting in.
What is the Universe?

Universe = system + surroundings
Energy is conserved: any energy lost by

the system is gained by the surroundings =
1st Law Thermodynamics
7
Thermochemistry
enthalpy change
Measuring Heat…
Heat versus Temperature

A “thought” experiment:
20ºC 20ºC
Full pan Almost empty pan
Heat Capacity (C and c)

So the more you have of a substance, the less the
*
temperature will rise for a given input of heat…
* In addition, different substances will change temperature

by a different amount (e.g. copper vs ceramic)
q = constant x T
The “constant” must be mass (or moles) dependent, and
be different for different substances…
m = mass of substance (g)

q = m c T n = amount of substance (mol)
c = specific heat capacity (J g-1 K-1)
q = n C T C = molar heat capacity (J mol-1 K-1)
8
A Thought….…
• If there was no WATER on the earth but only
ROCK…..
….it would take only 0.7 J of energy to
increase the temperature of each g of rock
by 1 K.
…this would result in high daytime
temperatures.
…it would also result in freezing
temperatures at night.
Heat Capacity
• Using the equation: q = c  m  T,
– you can determine the heat capacity of a
substance if the change in temperature
is known,
OR
– If the heat capacity of a substance is
known then you can calculate the “heat”
energy transferred to/from the
surroundings.
9
Determining the Specific Heat
Capacity of an Unknown Solid
• And q = c  m  T, where:
 q = heat, J
 c = heat capacity, J/g∙K, J.g-1K-1
 m = mass, g
 T = temperature, K
• NB: The heat of the system is numerically

equal to the heat of the surroundings but
opposite in sign: -qsolid = qwater
Specific Heat
Capacities
Q: How much energy (heat) does it
take to heat an Al saucepan (0.200 kg)
containing 1.00 L of water from room
temp. (20.0ºC) to boiling? Assume
thermal equilibrium between the pan
and water at all times.
Calculation:
q=
= (1000 x 4.184 + 200 x 0.9) x 80
= 3.49 x 105 J (349 kJ)
Specific Heat Capacity

Consider….
• Lucy finds a cut stone on the footpath that looks remarkably
like a diamond. In her enthusiasm she uses her 1st year
chemistry knowledge to determine its heat capacity. She heats
the 0.500 g stone to 477.0 C and plunges it into 20.0 mL of
water housed in a coffee cup calorimeter. The temperature of
the water increases from 22.2 – 23.7 C. Assuming all the heat
is transferred to the water, determine the heat capacity of the
stone. NB. cdiamond = 0.519 J.g-1K-1, czirconia = 0.214 J.g-1K-1.
10
Working
So where are we now…..

•So far we have only considered:
U = q
• First Law of Thermodynamics (Simple version)
• measuring heat provides U (calorimetry)
• tabulating U allows estimates of heat
BUT WAIT!!!!!.......THERE’S MORE!!!!!!!!
Energy is the capacity to produce heat.

Energy is also the capacity to do work.
Thermochemistry
enthalpy change
11
Lets build on what we know…
Recognition that there are other types of energy
In each case, which has higher potential energy?
Other types of energy

Other types of energy:
Type chemical example field equation
electrical battery electrochemistry E=VIt
light “glow stick” photochemistry E=h
piston engine thermochemistry E = -P V
spring rubber band mechanics E = ½ k x2
Exercise: Convince yourself in each case that the equation above has
units of energy (J). You will need to look up unknown symbols and their
units in any First Year Chem text.
[ Joule = kg m2 s-2 ]
Other types of energy

• electrical
• light We call these
• piston “work” (w)
•spring
First Law of Thermodynamics:

Simple version: U = q
Full version: U = q + w
12
Thermochemistry
So, if we leave until later…
Electrochemistry (next session)
Photochemistry (2nd & 3rd year chem)
Mechanical energy
Then we only consider, for now, w = -P V
So… U = q – P V
In words… when the internal energy changes in a reaction it
produces (uses) heat and pressure/volume changes in the
products.
Other types of energy…

SO….the energy changes in a chemical reaction are not
confined to one type of energy:
C8H18 (l)+ 12.5 O2 (g)  8 CO2 (g) + 9 H2O (g)
U = q U = q + ?
from Silberberg, p.227
An Example:
Q. When gas burns in an engine, the heat
released causes the CO2 and water vapor to
expand, pushing the pistons outwards.
Determine the change in energy in J and kJ
if the expanding gases do 451 J of work on
the pistons and if the system loses 325 J to
the surroundings as heat.
13
Thermochemistry
enthalpy change
Enthalpy
Recall…… U = q – P V
Rearrange… U + P V = q  H
ENTHALPY or
H =
HEAT OF REACTION
It is the experimentally observed heat change

for a chemical reaction under conditions of
constant pressure.
Notice: under conditions of constant volume, H = U
Enthalpy
Why is this so important?
Many practical chemical reactions are performed under constant
pressure, rather than constant volume conditions, for example:
• laboratory experiments in open containers
• biological reactions in living systems
• atmospheric reactions
• combustion reactions
So, if you were to measure the heat change in the reaction, you would be
measuring H, not U
Therefore 1. At constant P, calorimetry gives H

2. Tables of H predict heat change under experimental cond’ns
Additional Note: Even for gases, H and U are very close
14
Calorimetry
At constant pressure, the “coffee-cup”
calorimeter measures the heat of reaction, H.
• thermally insulating
• usually used for liquids
• esp. good for
• heat of dissolution
• heat capacity of solids
• aqueous reactions
Your prac class in week 10

What is a System?
• The region where the reaction is taking place
What are the Surroundings?

• The region outside the system,
ie. A water bath that the reaction
vessel is sitting in.
What is the Universe?

Universe = system + surroundings

Open system: exchange of
both matter and energy with
surroundings.
Closed system: fixed amount
of matter but energy can be
exchanged with the
surroundings.
Isolated system: No contact
with surroundings: hot
coffee in a vacuum flask.
15
Calorimetry
At constant volume, the “bomb” calorimeter
measures the internal energy change, U
(PV = 0 therefore q = U)
• thermally insulating
• usually used for
combustion reactions
• must know the heat
capacity of the
calorimeter.****
Relationship between H and U

• We just saw that the bomb calorimeter (constant
volume) and the coffee cup calorimeter (constant
pressure) measure two slightly different things.
Remember U + P V = q  H
• At constant volume, q = U
• At constant pressure, q = H
But what does this mean???

If we use a bomb calorimeter to measure q for
glucose, we are measuring U, internal energy BUT if
we want to know how much energy glucose will provide
for our bodies, we need to look at constant pressure!
And we need the enthalpy of reaction, H.

• For reactions where no gas is produced or
consumed, little expansion work will be done.
• Hence the difference between H and U will
be negligible so we assume that H = U.
• But if a gas is formed, work will be done.
• Hence we need to use the ideal gas equation
to relate H and U.
Remember U + P V = q  H
You will recall from gases that: PV = nRT
U + nRT = H,
where n = nfinal - ninitial
16
U + PV = q  H
Coffee-cup Bomb Calorimeter
Calorimeter

So how can we use this….
Q: A constant-volume calorimeter showed that the
heat loss accompanying the combustion of 1.000 mol
glucose molecules in the reaction:
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(g)
is 2559 kJ at 298K. What is the change in enthalpy
for the same reaction?
Ans:
ANS: The reaction must

produce a large amount
of energy (exothermic),
released in the form of
a pressure wave (i.e.
PV-type work is done)
Building demolition,
Boston
17
Which of the following would make a good explosive?
A) C3H5N3O9 (l )  1.5N2(g) + 3CO2(g) + 2.5H2O(g) + 0.25 O2(g)
B) CaCO3(s)  CaO(s) + CO2(g)
+
C) BrO3¯(aq) + 5Br¯(aq) + 6H3O (aq)  3Br2(aq) + 9H2O(l)
D) C7H5N3O6(s)  6 CO(g) + 2.5 H2(g) + 1.5 N2(g) + C(s)
Thermochemistry
enthalpy change
Enthalpies of common reactions

Enthalpy of combustion:
e.g. BBQ fuel (butane)
C4H10 (g) + 6.5 O2 (g)  4 CO2 (g) + 5 H2O (g) Hcomb = -2877 kJ mol-1
Enthalpy of atomisation:
e.g. butane
C4H10 (g)  4 C (g) + 10 H (g) Hatom = +5544 kJ mol-1
Enthalpy of formation:
eg. ethanol
2C(graphite) + 3 H2(g) + ½O2(g) → C2H5OH(l) Hf = -277.69 kJ mol-1
(s)
18
Standard Reaction Enthalpies
• An enthalpy reaction also depends on the conditions that
the expt is performed under. For example the pressure will
influence the enthalpy.
• For this reason, all reaction enthalpies in data booklets are
reported for reactions in which the reactant and products
are in their standard state…the form they are in at 1 bar,
eg water exists as a liquid at 1 bar, rm temp.
• Also standard reaction enthalpies are reported for
25 C = 298.15 K.
• The standard conditions for an aqueous solution are also
1 M.
• Now we can tell if the reaction enthalpy is for

standard state conditions because it is written as:
Hr.
Heats of Formation
• The heat of formation for an element
in its standard state is 0:
– eg Hf Ca(s) = 0
• A formation reaction is the reaction of
the elements in their standard state
added together to give the desired
product:
• Hf CaO(s) = -635.1 kJ/mol
corresponds to the equation:
• Ca(s) + ½ O2(g) → CaO(s)
Other tables can be found in

your text and in your SI data
book under properties of
These are in their inorganic or organic
standard state. compounds.
Standard Enthalpies of Formation

• The standard enthalpies of formation can also be used to determine
the enthalpy of a reaction using the following equation:
Hr = nHf(products) - nHf(reactants)

Example:
2 NH2CH2COOH(s) + 3O2(g) → H2NCONH2(s) + 3CO2(g) + 3H2O(l)
19
Enthalpies of common reactions
We also know that heat is also associated with
reactions of physical change.
For instance:
Enthalpy of fusion:
Eg. Ice (H2O(s)) melting
H2O(s) → H2O(l) Hfus = +6.01 kJ.mol-1
Enthalpy of vaporization:
e.g. H2O at 100 oC
H2O (l)  H2O (g) Hvap = +40.7 kJ mol-1
If we consider the same reaction from 25C, H = 44.0 kJ.mol-1
Enthalpy of special reactions

This process can be explained in a heating curve:
From Atkins and Jones, Fig 6.26.
Standard enthalpies of physical change
From Atkins and Jones
20
Standard Reaction Enthalpies
• Consider the H for the two reactions shown below.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) H = -802 kJ

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) H = -890. kJ
• Why are they different?

• In the first reaction the water is produced as a gas but
in the second it is produced as a liquid.
We also know from 2 slides ago that Hovap = 44 kJ.mol-1 ,
hence for 2 moles Hovap = 88 kJ
This explains the difference between the 2 reactions.
We will come back to this later……
Lets look a bit closer still…

• At standard temp and pressure the reaction
enthalpy for the reaction:
CH4(g) + 2O2(g) → CO2(g) + 2 H2O(l) Ho = -890kJ
• The enthalpy change refers to the equation as it
is written, that means that H = -890 kJ is the
reaction for 1 mole of methane and 2 moles of
oxygen.
• Hence if I double the reactants and products,
what does this mean for H??
Lets look a bit closer still…

• At standard temp and pressure the reaction enthalpy for
the reaction:
CH4(g) + 2O2(g) → CO2(g) + 2 H2O(l) H = -890kJ
• What happens if we turn the reaction around?
21
So let’s determine Ho from experimental
data…..
• Benzene (0.113 g) is burnt in excess oxygen in a
calorimeter with a heat capacity of 551 J (C)-1 and
the temperature rises by 8.60 C. Calculate the
reaction enthalpy for 1 mole benzene.
1. Write out the reaction:
2. Does the temperature rise or fall??
3. Next work out qcal
4. Now q = -qcal, therefore q = -4738.6 J
So let’s determine Ho from

experimental data…..
• Benzene (0.113 g) is burnt in excess oxygen in a
calorimeter with a heat capacity of 551 J (C)-1 and
the temperature rises by 8.60 C. Calculate the
reaction enthalpy for 1 mole of benzene.
5. But this is for 0.113 g benzene, how many moles is
this?
6. OK… but what then would be the H for the

combustion of one mole of benzene?
Bond enthalpies
Silberberg Table 9.2
22
Bond enthalpies and Hatom
The atomisation enthalpy is the sum of the
individual bond enthalpies:
Q: What is Hatom for methanol?
Hatom to estimate Hc

CH4(g) + 2 O2(g)  CO2(g) + 2 H2O (l); Hc = ?
All units kJ mol-1
Adapted from Silberberg, p.369
Hatom to estimate Hc

In chemical language:
kJ mol-1
CH4 (g) + 2O2 (g)  C (g) + 4 H (g) + 4 O (g) H = 2648

C (g) + 4 H (g) + 4 O (g)  CO2 (g) + 2 H2O (g) H = -3468
CH4 (g) + 2O2 (g)  CO2 (g) + 2 H2O (g) Hc = -820
This is called HESS’S LAW

In words… If you add up chemical equations to form a new (overall)
equation, then the overall enthalpy is the sum of the enthalpies.
Note: Using Hatom to estimate reaction enthalpy is only

approximate (a “simple” level of understanding)
23
Hess’s Law
Hess’s Law is one of the most important Laws
of chemistry. It allows us to estimate
thermodynamic quantities for reactions we
haven’t (or can’t) measure.
It doesn’t only apply to atomisation: H (kJ/mol)

CO (g) + ½ O2 (g)  CO2 (g) -283.0
NO (g)  ½ N2 (g) + ½ O2 (g) -90.3
CO(g) + NO(g)  CO2(g) + ½ N2(g) -373.3
Lattice Energies
• So let’s consider an ionic salt, for example
potassium chloride.
• We know from our previous lectures, that it is
an array of positive and negative ions.
• We also learnt that these ions are held
together by an energy…
– The lattice Energy
which is defined by the charge and distance between
the atoms.
Born-Haber Cycle
• For a given solid, the difference in molar
enthalpy between a solid and a gas of widely
separated ions is called the lattice enthalpy
of the solid, HL.
HL = Hm(ions,g) – Hm(solid)
• So…the lattice enthalpy can be identified by

the heat required to vaporise a solid into its
ions at constant pressure.
24
Born-Haber Cycle
• Lattice enthalpy of a solid cannot be
measured directly…..
…………So what could we do???
We can use:
Hess’s law
the first law of thermodynamics
And remember that enthalpy is a state function
Born-Haber Cycle
So let’s have a go…..
Devise a Born-Haber cycle to calculate the lattice
enthalpy of potassium chloride
Approach:
K+(g) + e(g) + Cl(g)
K+(g) + Cl(g)
Enthalpy
Lattice Energy
KCl(s)
25
Texas City docks,
Galveston
16th April, 1947
Texas fertiliser plant,

17th April, 2013
Thermodynamics
Part 2
Dr Carolyn Dillon
Consultation: carolynd@uow.edu.au
By appointment, email for on
campus consult, Rm 18.129 OR
See moodle for online times and
zoom link.
Thermodynamics
Reactions:
How hot thermochemistry
How likely thermodynamics
How fast
kinetics
How far
equilibrium
1
Thermodynamics
Energy spontaneously disperses

if it is not hindered from doing so.
Types of energy
Potential (Ep)
Ep
Kinetic (Ek)
2
Thermodynamics and the
Facts of Life
• Hot objects cool down

• Iron rusts
In
In each case:
each case:
• Sugar dissolves in water Where

Theseisprocesses
the energy
• Cars disintegrate on impact coming from?
are
• Air escapes from a balloon
• Batteries go flat Where is the energy
SPONTANEOUS
going to?
• Paper burns in oxygen
• There is always cleaning to do
How to be Spontaneous in
Chemistry
A spontaneous process has a tendency to occur
– it does not necessarily take place rapidly

– or instantaneously
– or at all on a human timescale
– but once started, however, it is self-
sustaining
It has nothing to do with speed (That’s kinetics!)

H2 + O2 will react to give water and we can mix the two
and they will be stable for millenia. But, add a spark……
3
Blocking the Spontaneous
Reaction
A spontaneous process can be prevented from
occurring by:
– Physical means:
• Holding onto a ball to prevent it rolling down a hill
• Closing a valve to prevent gas escaping into a
larger volume
– The Activation Energy (Ea) of a reaction

which is linked to temperature.. (see kinetics
lectures later).
Blocking (T) the Spontaneous

Reaction
Once these means are overcome, the reaction or

process is self-sustaining: spontaneous.
Brown, et al. Ch 14, p 528
4
How to be nonspontaneous
• Nonspontaneous processes:
– Driving a gas into a smaller volume by pushing down

a piston (e.g. Bike pump, E = P V)
– Charging mobile phone batteries by plugging them

into a source of electricity (E = ItV)
– Heating objects up by placing them over a Bunsen

flame (E=mCT).
Work must be done and none of these are self-

sustaining
Spontaneous vs non-spontaneous
Processes
that are
spontaneous
in one
direction
are non-
spontaneous
in the
reverse
direction.
No energy change
Energy Change
No PV
5
Thermodynamics
Energy spontaneously tends to flow from
being concentrated in one place to
becoming diffused or dispersed and
spread out –
if it is not hindered from doing so.
Energy Disperses two ways…

Consider…
How much Energy disperses?
– Hot objects cool down
But often there is no change in energy content of the

system, what then?
How widely does the Energy disperse?

– Sugar dissolves in water
– Ne and Ar gas mixing – ideal gas
– Or Butan-1-ol and butan-2-ol ideal soln
6
Entropy, S
S = Sfinal  Sinitial Entropy is a state function
Most likely (highest entropy)
Least likely (lowest entropy)
Entropy, S
In chemistry, the energy that entropy

measures is:
Phase change energy

(enthalpy of fusion and vapourisation)
and
Motional energy
(translational, rotational and vibrational)
7
S – Measuring the Energy that
Disperses
• How much energy is dispersed?

(at a specific Temperature)
or Isothermal
Process
• How widely spread out has this
energy become?(at a specific Temperature)
Entropy: Exactly how do we

measure it?

“energy dispersed”
Entropy change =
T
qrev –1
S = J·K
T
What happens to T when you add energy?
8
Enthalpy of physical change
The heating curve for water:
40.7 kJ·mol-1
Temperature (°C)
ΔHvap
100
H-bonds, dipole-dipole,
London, etc
ΔHfus
Overcoming
0
intermolecular forces
Solid Liquid Vapourisation Gas
Heat Added

measure it?
9
measure it?
Entropy change: amount of energy that has been
spread out in the water so it could change to steam
divided by temperature (qrev = 40.7 kJ/mol, T = 373K)
Thermodynamics : How
Entropy changes with T
Absolute Entropy, S (J·K–1)
Solid Liquid Gas
At absolute
zero the
Vapourisation
entropy is
zero
Melting
0
0
Temperature (K)
10
Entropy, S
In chemistry, the energy that entropy

measures is:
Phase change energy

(enthalpy of fusion and vapourisation)
and
Motional energy
(translational, rotational and vibrational)
Standard Entropy of a
substance
11
Thermodynamics – Which has
the higher S0?
(A) Hg (l) at 298 K
(B) Hg (g) at 298 K

the higher S0?
(A) Li (s) at 298 K
(B) U (s) at 298 K
12
the higher S0?
(A) H2O (l) at 298 K
(B) H2O (l) at 323 K
S – Measuring the Energy that

Disperses

or
• How widely spread out has this energy

become? (at a specific Temperature)
This measurement is the

change in Entropy, S
13
measure it?
The S change in entropy when:
a gas expands into a vacuum
or
when two ideal liquids / two ideal gases
mix
or
when a perfect solute dissolves in a
solvent
In these examples, there is an increase in entropy.
Thermodynamics
The entropy of the universe always

increases
Suniverse > 0
The 2nd Law of Thermodynamics
14
Thermodynamics - the 2nd Law
Suniverse (= Ssystem + Ssurroundings) > 0
Ssystem = Sproducts - Sreactants
Ssurroundings = -H/T
Which reaction has the higher

S?
Ssystem = Sproducts - Sreactants
(A) 2NI3 (s) → N2 (g) + 3I2 (g)
(B) 2Mg (s) + O2 (g) → 2MgO (s)
(C) 2H2O2 (l) → 2H2O (l) + O2 (g)
15
Thermodynamics - the 2nd Law
Suniverse (= Ssystem + Ssurroundings) > 0
 When hot objects cool down or water freezes?

 When Iron rusts?
4 Fe(s) + 3 O2 (g)  2 Fe2O3 (s)
Problem
Calculate the total entropy change for the
following reaction under standard conditions:
NH3 (g) + HCl (g) → NH4Cl (s) H0 =  315 kJ
S0 (J/K mol)
NH3 (g) = 192.3
HCl (g) = 186.8
NH4Cl (s) = 94.6
16

CHEM103 Thermo Lectures 2024 Carolyn Dillon

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CHEM103 Thermo Lectures 2024 Carolyn Dillon

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Texas City docks,

Texas fertiliser plant,

What makes an explosive?

James Prescott Joule –

Energy Units = Joule

“Calories” vs. calories

Types of energy (molecular)

Chemical reactions and energy

N2O4 (g) + heat  2 NO2 (g)

Chemical reactions and energy

N2O4 (g) + heat  2 NO2 (g)

Chemical reactions and energy

Chemical reactions and energy

U > 0 heat products

Chemical reactions and energy

Therefore - measuring heat  U (calorimetry)

Systems and Surroundings

What are the Surroundings?

What is the Universe?

Energy is conserved: any energy lost by

Heat versus Temperature

Full pan Almost empty pan

Heat Capacity (C and c)

* In addition, different substances will change temperature

m = mass of substance (g)

• NB: The heat of the system is numerically

Specific Heat Capacity

So where are we now…..

BUT WAIT!!!!!.......THERE’S MORE!!!!!!!!

Energy is the capacity to produce heat.

In each case, which has higher potential energy?

Other types of energy

Other types of energy

First Law of Thermodynamics:

Then we only consider, for now, w = -P V

Other types of energy…

It is the experimentally observed heat change

Therefore 1. At constant P, calorimetry gives H

Your prac class in week 10

Systems and Surroundings

What are the Surroundings?

What is the Universe?

Systems and Surroundings

Relationship between H and U

But what does this mean???

Relationship between H and U

Relationship between H and U

What makes an explosive?

ANS: The reaction must

A) C3H5N3O9 (l )  1.5N2(g) + 3CO2(g) + 2.5H2O(g) + 0.25 O2(g)

B) CaCO3(s)  CaO(s) + CO2(g)

D) C7H5N3O6(s)  6 CO(g) + 2.5 H2(g) + 1.5 N2(g) + C(s)

Enthalpies of common reactions

• Now we can tell if the reaction enthalpy is for

Other tables can be found in

Standard Enthalpies of Formation

Hr = nHf(products) - nHf(reactants)

Enthalpy of special reactions

From Atkins and Jones, Fig 6.26.

Standard enthalpies of physical change

From Atkins and Jones

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) H = -802 kJ

• Why are they different?

Lets look a bit closer still…