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Welcome to CHEM1020! Welcome to CHEM1020!

Chemical Energetics & Reactivity Chemical Energetics & Reactivity


Module 1
Ch i l E ti Chemical Energetics
Lecturers: Prof Bob Gilbert b.gilbert@uq.edu.au
Dr Horst Schirra h.schirra@uq.edu.au
Prof Matt Trau m.trau@uq.edu.au
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Welcome to CHEM1020! Welcome to CHEM1020!
Ch i l E ti & R ti it Chemical Energetics & Reactivity
Text: Chemistry. Blackman, Bottle, Schmid, Mocerino and Text: Chemistry. Blackman, Bottle, Schmid, Mocerino and
Wille.
John Wiley. 2008
For the Electronic Course Profile see Blackboard
(http://blackboard.elearning.uq.edu.au)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
ALWAYS BRING A CALCULATOR + PAPER + PEN
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centre of the CHEM1020
universe!
Every Monday a course Bb
announcement will
summarise the weeks
i i i /d dli / i activities/deadlines/notices
A il ill t b t An email will not be sent
every time new information is
dd d Y t h k Bb added. You must check Bb
regularly.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Sign up for.
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Lecture notes & Lectopia for each stream will be
available on Blackboard (Bb) site. Hard copies available
for purchase from POD at back of UQ Coop Bookshop
Lecture timetable check on SI-net
Rooms may change up to Week 3!
P ti l 5 i t (3 h l ) Practicals: 5 x experiments (3 hrs long)
Induction sessions begin in week 1, sign up via SI-net &
manuals will be provided at 1
st
session. Consider
CASPiE URE as an alternative lab route.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
PASS (attendance very strongly recommended)
General Information General Information
Assessment Assessment
50% MCQ and SAQ exam at end of semester (must gain 40%
or higher in final exam to gain a grade of 4 or higher). g g g g )
20% practical work
12% 2 QUIZZES
18% IS IT Ch i t C ll b ti R h T k (b i i 18% IS-IT Chemistry Collaborative Research Task (begins in
week 2 details via Bb)
See ECP, POD lecture notes AND BLACKBOARD
(Bb) site for complete details of the course including
th t h d l the assessment schedule.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Course Coordinator: Dr Gwen Lawrie CHEM1020@scmb.uq.edu.au
eLearni ng f or St udent s eLearni ng f or St udent s
Bl ackboard Home: ht t p: / / bl ackboard. el earni ng. uq. edu. au
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Use Bl ackboard to obtain all course Announcements and Use Bl ackboard to obtain all course Announcements and
Course Resources
U th C P f i l li k f ll th d t il i t d Use the Course Prof i l e link for all the details associated
with your course.
Ph (07) 3365 8811
For st udent t echni cal support and f or Bl ackboard Trai ni ng
Phone: (07) 3365 8811
Emai l : hel p@aski t . uq. edu. au
W b ht t / / ki t d /
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
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Check Course Site on Bb frequently:
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the information that you require!
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My Grades Schedules and guidelines My Grades
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School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What's on!
Course coordinator: Dr Gwen Lawrie
g.lawrie@uq.edu.au
General Information QUIZZES General Information QUIZZES
These are online tests throughout the semester.
There are 2 QUIZZES and only 1 attempt at each There are 2 QUIZZES and only 1 attempt at each.
Each QUIZ is worth a maximum of 6% of the total course
mark. mark.
Full details are available under the new QUIZ menu link
Student Feedback 2009 & 2010: These QUIZZES are the best
preparation for the exam!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
General Information LABS General Information LABS
You must complete the induction in week 1 or 2.
You need to bring your own lab coat & safety glasses You need to bring your own lab coat & safety glasses
Tie up your long hair (both genders) and wear closed-in
shoes or you will be turned away. y y
f f All lab info and contacts for reschedules are provided
under the Lab Resources Menu Tab on Bb!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Collaborative Group Task (weeks 2-12):
Yo choose a scenario represent global science iss es You choose a scenario represent global science issues.
You will be working in Groups of 4
Groups are assembled by one of three ways (either
choose your team members; opt into a group; or be placed
by IS IT coordinator) by IS-IT coordinator).
Full details & sign on will be available in week 2 through
the IS IT Chemistry Menu tab on Bb the IS-IT Chemistry Menu tab on Bb.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What i s PASS?
PASS are Peer Assi st ed St udy Sessi ons PASS are Peer Assi st ed St udy Sessi ons
PASS provi des one hour of ment ored group st udy, where
you are abl e t o:
Cl ari f y concept s not f ul l y underst ood
Pract i ce quest i ons i n exam f ormat
Revi se your own l earni ng
Ident i f y gaps i n your own knowl edge
Pract i ce l earni ng i n t he l anguage of t he di sci pl i ne
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Be part of an i nt eract i ve l earni ng communi t y!
5 5
CHEM1020S22009
MeanGradesbyPASSAttendance
5.5
5
e
5
e
a
n

G
r
a
d
4.5
O
v
e
r
a
l
l

M
4.5
O
4
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
0(295) 14(251) 58(238) 9+(287)
PASSSessionAttendance#
CHEM1020S22009
GradeDistribution:EffectofPASSAttendance
45%
50%
35%
40%
25%
30%
u
d
e
n
t
s
15%
20%
S
t
u
5%
10%
0%
1 2 3 4 5 6 7
Grade
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Grade
0(295) 14(251) 58(238) 9+(287)
PASS Classes
begin in Week 3:
Monday August 8
th
Monday August 8
th

School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Strategies for learning quantitative chemistry
In module 1
Reading before lectures
In class model Qs
JITT b i (F db k)
In module 2
JITTerbug quizzes (Feedback)
In module 2
In-class problem-solving
Homework between lectures
I d l 3 In module 3
In-class problem-solving
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Homework between lectures
Module 1: 12 Lectures Module 1: 12 Lectures
1. States of Matter. Chapters 6 and 7 (p202 281)
- Gases and Gas Laws
- Intermolecular Forces
- Phase Changes
2. Thermochemistry. Chapter 8 (p281 331)
- The First and Second Laws
- Defining Internal Energy and Enthalpy
- Quantifying Enthalpy
- Defining Entropy
- The Gibbs Function
3. Equilibrium. Chapter 9 (p332 372)
- Chemical Equilibrium
- Equilibrium and Gibbs Free Energy q gy
- How systems at equilibrium respond to change
- Equilibrium calculations
L k f th i
= A Key Concept
Look for the icon
with page numbers!
= A worked example in the text book you should look at
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
ALWAYS BRING A CALCULATOR + PAPER + PEN
Energy: Energy:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
States of Matter States of Matter
What are the 3 states of matter What are the 3 states of matter
evident in this image?
Think Back!
How can we explain why some substances exist as gases at room
temperature and atmospheric pressure, but others are liquids or
solids? solids?
=> Forces t hat occur bet ween i ndi vi dual at oms,
l l i (i t l l f )
L t b i ith i th th i t
mol ecul es or i ons (i nt er mol ecul ar f or ces)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Lets begin with gases since they are the easiest .
Gaseous El ement s Gaseous El ement s
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
(Elements in their pure state are mostly solids, with exceptions)
Why do we look at gases? Why do we look at gases?
We must understand gases to understand and solve some
important problems:
Greenhouse Effect
P ll ti h t h i l Pollution, photochemical smog
Energy production
Acid Rain Acid Rain
Biochemistry of lungs
Scuba diving Scuba diving
What are the characteristics of gases?
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What are the characteristics of gases?
Characteristics of Gases
6.2, 203
Characteristics of Gases
A gas will expand to occupy all available space it is in and will
not form a separate surface Gases have no fixed volume or not form a separate surface. Gases have no fixed volume or
shape.
Atoms in a gas move independently of each other and move
randomly (Because the atoms in a gas are moving at random,
the gaseous state is the simplest to describe mathematically by
making some simple assumptions) making some simple assumptions).
Gases exert a pressure. Gases exert a pressure.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Gas Pressure Gas essu e
Gas molecules are in constant motion and collide with each other and the
container walls container walls
they exert a pressure on the surroundings.
The number of collisions/unit area = Force/unit area = Pressure The number of collisions/unit area = Force/unit area = Pressure
The pressure is defined as: p =
FORCE (N)
AREA (m
2
)
A
F
AREA (m )
O i f
Gas molecules have mass
(m) and velocity (v)
O i f
Gas molecules have mass
(m) and velocity (v)
Opposing force Opposing force
SI Units:
N
1 Pa (pascal)= 1 N m
-2
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
SI Units:
2
m
1 Pa (pascal)= 1 N m
2
Gas Pressure
SI Units:
Gas Pressure
SI Units:
1 Nm
-2
= 1 Pascal (Pa) = 1 J m
-3
( )
You are going t o come across ot her unit s:
Atmosphere (atm)
1atm = 1.01325 10
5
Pa (101.325 kPa)
= 760 mm Hg (= 760 Torr) g ( )
= 14.696 psi (pound per square inch)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Import ant ! St andard Condi t i ons (STP)
Standard temperature = 0
o
C = 273 K
Import ant ! St andard Condi t i ons (STP)
Standard temperature 0 C 273 K
Standard pressure: Two definitions:
1 atmosphere = 100 000 Pa (IUPAC + Blackman Chemistry)
Standard concentration = 1 mol L
-1
(M) Standard concentration = 1 mol L
1
(M)
SI units:
Pressure = Pa Pressure = Pa
Temperature = K
Volume = m
3
(10
3
dm
3
or 10
3
L)
Sometimes we need to stop
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
( )
Sometimes we need to stop
and think about units!
The Ideal Gas Equation e dea Gas quat o
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Ideal Gas Equat i on
6.2, 205
The Ideal Gas Equat i on
V RT Id l G E t i pV = nRT Ideal Gas Equat i on
One of the most important equations in physical chemistry.
Describes how an i deal gas behaves under given conditions of
pressure volume and temperature
p = pressure (Pa or atm)
pressure, volume and temperature
V = volume (m
3
or L)
n = molar amount of gas (mol)
T temperature (K)
1 1
1 1
l K t L 0 082057
) ( mol K J 8.314

= SI R R = gas constant
T = temperature (K)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
1 1
mol K atm L 0.082057

=
Assumptions in the Ideal Gas Law?
6.2, 211-13
p
The molecules are very small compared to the distance between
th ( th h li ibl l ) them (= they have negligible volume).
The molecules do not see each other (= no intermolecular
interactions.
The molecules undergo elastic collisions with container walls (= no
energy is lost due to the collision).
The molecules move in completely random motion (different speeds p y ( p
and direction).
> D fi iti f Id l G => Definition of an Ideal Gas:
If a gas meets these conditions then it will obey
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
g y
pV = nRT, and it is Ideal
Wh t d th Id l
6.2, 204 - 205
What does the Ideal
Gas Equation tell us?
H d th f h h th How does the pressure of a gas change when we vary the
volume, temperature, or amount of gas (number of moles)?
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Usi ng t he Ideal Gas Equat i on Usi ng t he Ideal Gas Equat i on
Suppose we change any of the variables: Suppose we change any of the variables:
1 1
Initially
V p
R =
1 1
Initially
T n
R =
2 2
Finally
T
V p
R =
2 2
y
T n
2 2
2 2
1 1
1 1
T n
V p
T n
V p
=
If one variable remains
constant it cancels
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2 2 1 1
T n T n constant, it cancels.
Example
A sample of helium gas is held at constant temperature inside a cylinder
with a volume 0.57 L. The external pressure is 2.1 x 10
5
Pa. If the piston is
p
withdrawn until the gas volume is 2.55 L. Calculate the final pressure.
Apply the ideal gas law to the initial and final conditions Apply the ideal gas law to the initial and final conditions
the no of moles of He & T are constant in this problem
p
1
V
1
= p
2
V
2
and rearranging to: p
2
= p
1
V
1
V
2
p
2
= (2.1 x 10
5
Pa) x (0.57 x 10
-3
m
3
) = 0.47 x 10
5
Pa
3 3
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2.55 x 10
-3
m
3
Units! 1 L = 1 x 10
-3
m
3
When applying the ideal gas law to solve problems: When applying the ideal gas law to solve problems:
1. Watch out for units:
If R is 8.314 J K mol
-1
, p is Pa (Jm
-3
or Nm
-2
) and V is m
3
If R is 0.08206 L atm K
-1
mol
-1
, p is atmos, V is L
Temperature is in Kelvin Temperature is in Kelvin
2. A useful value (by substituting into the ideal gas law):
1 mole of gas occupies 22.4 L @ 273 K & 1 atm
or 24.5 L @ 298 K & 1 atm
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Anot her Exampl e Anot her Exampl e
A sample of chlorine gas occupies a volume of 946 mL at a pressure
of 726 mmHg. Calculate the pressure of the gas if the volume is
reduced to 154 mL (assume temperature remains constant)
Sol ut i on: Since pV = nRT = constant,
p
1
V
1
= p
2
V
2
, hence
mL 946
H 726
2
1 1
2
=
V
V p
p
Hg mm 10 4.46
mL 154
Hg mm 726
3
=
=
kPa 101.3
Hg mm 760
Hg mm 10 4.46
3
2

= p
or to convert to Pa:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
kPa 594 =
CHEM1020 CHEM1020
Module 1: Lecture 2
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
G d Ab l t T t
6.2, 204
N t th t th i t t f h li li t 273 15C k b l t
Gases and Absolute Temperature
P
Note that the intercept of each line lies at -273.15C, known as absolute
zero.
0 K = -273.15 C
V
P
1
P
2
P
3
Absolute Zero
T (C) -273.15 C
Absolute zero: the lowest temperature that can be. It is theoretical and has
not been reached (Liquid Helium gets to 4 K). All calculations done using
the temperature scale of Kelvin; the lowest temperature is 0 K (NO
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
the temperature scale of Kelvin; the lowest temperature is 0 K (NO
negative values).
Absolute Temperature Absolute Temperature
Kelvin: absolute temperature scale.
(Room Temp) 25 C 298 K
0 K = -273.15 C
T (K) = T(C) + 273 15 T (K) = T(C) + 273.15
Note: many of the equations we Note: many of the equations we
will use require the use of temperature
in Kelvins.
Also note: Temperature differences are the same in Kelvin or C
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example: Example:
Suppose we have a 12.2 L sample containing 0.50 mol oxygen gas at
pressure of 1 atm. If all this oxygen were converted to ozone (O
3
) at
T d P h t ld b th l ? same T and P, what would be the volume?
) ( 2O ) ( 3O
3 2
g g ) ( 2O ) ( 3O
3 2
g g
No. moles O
3
produced =
3
2
O mol 3
O mol 2
O mol 0.50
2
O mol 3
= 0.33 mol O
3
Since V/n is constant,
2
2
1
1
n
V
n
V
=
1
2
1 2
|
|
.
|

\
|
=
n
n
V V
L 8.1
L 12.2
mol 0.50
mol 0.33
=
=
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example of application of ideal gas law: Example of application of ideal gas law:
Air Bags
Sodium azide decomposes rapidly
(explosively) to produce nitrogen (explosively) to produce nitrogen
gas.
2N N ( ) 2N ( ) 3N ( ) 2NaN
3
(s) 2Na(s) + 3N
2
(g)
Causes inflation in < 0.05s
How many litres of nitrogen would
100g NaN
3
produce at room temp
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
www.howstuffworks.com
g
3
p p
and pressure?
2N N ( ) 2N ( ) 3N ( ) 2NaN
3
(s) 2Na(s) + 3N
2
(g)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Additional uses of the Ideal Gas Equation
6.4, 214/215
Determination of molar mass (M
R
)
Additional uses of the Ideal Gas Equation
(
R
)
Number of moles (n) = mass/molecular weight = m/M
R
pV = nRT <=> pV = m/M
R
RT <=> M
R
= mRT / pV
Determination of density Determination of density
= m/V
Using this equation and n = m/M
R
, we can rearrange pV=nRT to give:

gas
=
m
V
=
p M
R
RT
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Worked examples in Blackman 6.4 p214/5
Ki ti Th f G Kinetic Theory of Gases
The Ideal Gas Law provides a numerical route for predicting gas
behaviour based on macroscopic observations (changes in
pressure and volume).
Can we use the kinetic theory of gases to predict the same Can we use the kinetic theory of gases to predict the same
behaviour on a molecular basis?
Richard Feynman: Its all about atoms jiggling about!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Wh t d th Id l
6.2, 204 - 205
What does the Ideal
Gas Equation tell us?
H d th f h h th How does the pressure of a gas change when we vary the
volume, temperature, or amount of gas (number of moles)?
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Description of an ideal gas from a molecular p g
viewpoint.
Gas molecules have mass (m) and t
t
.
e
d
u
/
Gas molecules have mass (m) and
velocity (v) therefore have kinetic
energy:
/
/
w
w
w
.
p
i
t
E
kinetic
=
1
2
mv
2
r
t
o
n

h
t
t
p
:
/
kinetic
2
J
o
h
n

N
o
r
We assume that translational kinetic energy is the only internal
energy possessed by a gas molecule. (We ignore rotational,
J
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
gy p y g ( g ,
vibrational etc energy).
6.3, 208
E
kinetic
=
1
2
mv
2
Gas molecules are in constant
random motion. The energy of a
molecule is related to its speed.
There is a distribution of speeds, v, amongst a population
f l l
Most probable energy
of gas molecules.
o
l
e
c
u
l
e
s
Most probable energy
Mean energy
b
e
r

o
f

M
o
Kinetic Energy
N
u
m
b
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Kinetic Energy
Relationship between Kinetic Energy & Temperature Relationship between Kinetic Energy & Temperature
Experiments show that
molecules move faster as molecules move faster as
temperature increases
To find the average kinetic energy we add the individual
molecular kinetic energies and divide by the total number of
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
g y
molecules
6.3, 211
The resulting expression is:
E
kinetic
=
3RT
2N
The resulting expression is:
= kT
3
2
(kinetic energy of one gas molecule)
kinetic
2N
A
Multiply by N
A
to get average kinetic energy per mole of gas
2
( gy g )
E
ki ti l
=
3
RT
p y y
A
g g gy p g
This expression is independent
E
kinetic, molar
2
RT
of the identity of the gas!
Temperature: A measure of the average kinetic energy of a gas.
Th t t l ki ti i th th l The total kinetic energy is the thermal energy.
Important! Temperature and thermal energy describe different
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Important! Temperature and thermal energy describe different
properties!!
Kinetic Theory of Gases Derivation Kinetic Theory of Gases Derivation
Can we understand E = 3/2 kT from kinetic gas theory? Can we understand E
kin
= 3/2 kT from kinetic gas theory?
Molecules are in constant motion and collisions can occur between
l l ith th b d i f th t i molecules or with the boundaries of the container.
The number of collisions/unit area = Force/unit area = pressure
Elastic Collisions
v
x
before
x
v
x
before
after
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Derivation (for your information only)
L
F
Area
Force
p = =
2
El ast i c Col l i si ons
v
x
-v
x
before
ft
x
v v 2 = A
x
L
t
t
L
v = A
A
=
L
mv
L
v
v m
t
v
m ma F
x x
x i
= |
.
|

\
|
=
A
A
= = 2 2
2
x
after
x
x
v t A
Force of one particle hitting one side of the cube
V
mv
L
mv
L L
mv
L
F
p
i
i
= = = =
3
1
3
1
6
2
6
2
3
2
2
2
2
6 sides to a cube => pressure of one particle
mv nN pV
V
mv
nN p
V L L L L
A A
= =
3
1
3
3 3 6 6
2
2
This looks already like the ideal gas law
pressure from many particles:
E
nN
pV
V
kin
A
A A
= 2
3 3
kin kin
E mv mv E 2
2
1
2 2
= =
nRT pV
RT nN
pV
p
A
kin
= =
3 2
3
kin kin
2
kin
N
RT
kT E
2
3
2
3
= =
q e d
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
nRT pV
N
pV
A
= =
2 3
A
N 2 2
q.e.d.
Historically, it went the other way round
mv nN pV
V
mv
nN p
A A
3
1
3
2
2
= = This looks already like the ideal gas law
E
nN
pV
kin
A
2
3
=
kin kin
E mv mv E 2
2
1
2 2
= =
RT
n
pV
nRT pV = =
kT
N
RT
nN
pV
E
kin
2
3
2
3
2
3
= = =
=> Using the ideal gas law to
define absolute temperature in
N nN
A A
2 2 2
define absolute temperature in
terms of kinetic energy of
molecules
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Rates of gas movement
6.3, 217
Rates of gas movement
E
kinetic
=
3RT
2
E
kinetic
=
1
mv
2
and
kinetic
2N
A
kinetic
2
1 3RT
So
1
2
mv
2
3RT
2N
A
=
Solve for v (noting that mN
A
is the mass of 1 mole of
gas = M
R
)
R
M
RT
v
3
_
=
=> The heavier a gas molecule, the slower its
average speed! Important for understanding
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
average speed! Important for understanding
diffusion and effusion.
Can kinetic theory help us predict gas properties? Can kinetic theory help us predict gas properties?
An increase in temperature increases the speed of the An increase in temperature increases the speed of the
molecules and hence the number of collisions per unit area
and increases pressure (constant V & n)
Reducing the amount of gas molecules, n, decreases the
n mber of collisions per nit area red ces press re number of collisions per unit area reduces pressure
(constant V & T) or volume (constant p & T)
Think about the ideal gas equation and whether it Think about the ideal gas equation and whether it
can be explained in terms of kinetic theory!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
CHEM1020 CHEM1020
Module 1: Lecture 3
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Daltons Law of Partial Pressures
6.5, 219
Dalton s Law of Partial Pressures.
The total pressure of a mixture of gases is the sum of the pressures p g p
that each gas would exert if it were alone in the container.
p = p + p + p p
p = partial pressures
p
T
= p
1
+ p
2
+ p
3
.p
i
p
i
= partial pressures
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
www.kentchemistry.com/links/GasLaws/dalton.htm
Why??
If a sample contains gases A and B, the total pressure is given by:
Why??
p
t
=
n
T
RT
V
= RT (n
A
+ n
B
)
V
= n
A
RT + n
B
RT
V
A B
V V
= p
A
+ p
B
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
How does the pressure of one gas relate to the total ??
p
A
n
A
RT/V
How does the pressure of one gas relate to the total ??
p
A
p
T
=
(n
A
+ n
B
)RT/V
=
n
A
=
p
A
+ p
B
(n
A
+ n
B
)
=
x
A
100%A
x
A
is the mole fract ion of A, x
A
: 0 1
100% A
Hence:
p
A
= x
A
p
T
x
A
0 1
Hence:
p
B
= x
B
p
T
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
In general for component i: p
i
= x
i
p
T
.
Q ti Question:
A SCUBA diver is using EANx32, an enhanced
Nitrox gas mixture. This mixture contains 32%
Oxygen with 68% Nitrogen. If the cylinder is at
a pressure of 250 kPa what is the partial
pressure of Oxygen? p yg
http://www.oceanearth.org/pastinfo.html
Mole fraction of oxygen = 0.32
p
O2
= 0.32 x 250 kPa
= 80 kPa
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Deep sea divers use helium instead of nitrogen (Heliox) why?
What you should be able to do at this stage: a you s ou d be ab e o do a s s age
1. List the qualities that define an ideal gas. q g
2. Describe ideal gas behaviour in terms of the relationship
between p, V, n and T (macroscopic). between p, V, n and T (macroscopic).
3. Apply the ideal gas law pV = nRT
4. Explain how and why kinetic energy influences p, V and T
(microscopic).
5. Understand the difference between t emperat ure and t hermal
energy.
6. Describe how the partial pressures of individual gases in a
mixture influence the total pressure
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
mixture influence the total pressure.
What about Real Gases?
The ideal gas law begins to
b k d t l t t break down at low temperatures
or pressures.
Why?
Because gas molecules possess
l d h a volume and can see each
other (=intermolecular
interactions)
Solution?
Modify the ideal gas law to incorporate corrections for real gases
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
=> e.g. van der Waals Equation (2
nd
year)
6.7, 226
St t f M tt i t l l f
As gas molecules lose kinetic energy (lowering of T) or experience
States of Matter intermolecular forces
As gas molecules lose kinetic energy (lowering of T) or experience
increased numbers of collisions (increase in p), intermolecular
forces become more relevant.
I nt ermolecular forces are the forces that occur between molecules.
A chemical bond is not an intermolecular force (int ramolecular
force)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
force).
Types of Intermolecular Force Types of Intermolecular Force.
This should be revision - remember Chem1030 &/or senior chemistry??
Three types of molecular force depending on molecule polarity:
This should be revision remember Chem1030 &/or senior chemistry??
yp p g p y
1.Dispersion Forces.
2.Dipolar forces.
3 Hydrogen Bonds 3.Hydrogen Bonds.
Relative Strength:
Dispersion forces < Dipolar forces < Hydrogen Bonds
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
6.8, 231
Di pol e-di pol e i nt eract i ons
Molecules with dipole moments can line up so that negative
d iti d l l d t l t t ti
Di pol e di pol e i nt eract i ons
and positive ends are close leads to an electrostatic
attraction. Generally important over short distances.
A dipole on a molecule arises from the combination of molecular
( )
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
shape and bond polarity (revise).
London di spersi on (or van der Waal s) f orces London di spersi on (or van der Waal s) f orces
Why do non-polar atoms or molecules exist in condensed states
under some conditions?
For example helium exists as a liquid below about 4 K.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
phys.kent.edu
6.8, 229
Transient changes in the charge
distribution around a nucleus (or distribution around a nucleus (or
molecule) can occur, and when this
happens near another atom, the
dipole can induce a dipole in the dipole can induce a dipole in the
other atom.
This results in a weak and short-
li d i t ti k L d lived interaction known as London
dispersion force.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Some general physical properties can be related to
6.8, 231
Some general physical properties can be related to
Intermolecular Forces
Halogens are diatomic (F
2
) and interact
via DISPERSION forces.
More electrons = more easily
polarisable = stronger bond
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
6.8, 233
Hydrogen Bondi ng
Hydrogen bonds are a special form of dipolar forces. Due to
hi hl l b d ( O H) i h l d fi i
Hydrogen Bondi ng
highly polar bonds (e.g O-H) with an electron deficient
hydrogen, and the small size of hydrogen. Usually involve H
attached to O, N or F.
A network of H-bonding
can be very strong
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
can be very strong.
7.1, 243
Intermolecular Forces in Liquids
Surface Tension.
Intermolecular Forces in Liquids.
Molecules in a liquids experience q p
attractive forces from other molecules,
but molecules at the surface experience
uneven forces surface t ension. uneven forces surface t ension.
The surface area stays as small as
possible possible.
Cohesive forces: attract molecules in Cohesive forces: attract molecules in
the liquid to one another.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Intermolecular Forces in Liquids.
Capillary action.
q
Adhesive forces: attract
molecules in the liquid to the
walls of the container.
Capillary action occurs when
the adhesive forces are
encarta.msn.com
stronger than cohesive forces
and gravity.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Intermolecular Forces in Liquids.
7.1, 244
Vapour Pressure
S l l bl t f th f
q
Some molecules are able to escape from the surface
of the liquid. These gaseous molecules exert a pressure.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Intermolecular Forces in Solids.
7.2, 245
Intermolecular Forces in Solids.
In solids, intermolecular forces are so strong that there is no
l l t f l l large scale movement of molecules.
Amorphous no extended order
Solids
(e.g. glass, plastics)
Crystalline highly ordered y g y
(e.g. diamond)
In liquids the boiling point tells us about strength of
intermolecular forces. In solids, it is the melt ing point .
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
See table 7.1, pg 246
Intermolecular Forces in Solids
7.2, 246
Intermolecular Forces in Solids.
Molecular solids are materials in which individual molecules occupy Molecular solids are materials in which individual molecules occupy
lattice positions (eg ice). Intermolecular forces are relatively much
weaker than the covalent int ramolecular forces.
Sugar
Dry Ice
Napthalene
The molecules are typically bound by dispersion, dipolar or H-bonds.
Generally low melting temperatures
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Generally low melting temperatures
Bonding in Solids
7.2, 247
Bonding in Solids
But, there are other solids where bonding is very strong:
1 Network 1. Network
2. Metallic
3. Ionic solids.
Strength: Strength:
Network > Metallic > Ionic
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Bonding in Solids
7.2, 247
Net work solids ( highest melt ing point ) .
g
Network solids have a array of covalent bonds which
links each atom to its neighbouring atoms.
The extent of covalent bonding influences properties.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Diamond Graphite
Carbon solids Carbon solids
sp
3
dispersion
3550C
Diamond Diamond
sp
2
Graphite
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
encarta.msn.com
Buckyballs
7.2, 248
Bonding in Solids
Met allic solids.
g
Bonding in metals is characterised by non-directional covalent
bonding.
Electrons (covalent ) are arranged around metal atoms in such a
way that they are mobile (non- direct ional).
Why are the electrons delocalised?
When two metal atoms interact, two molecular orbitals result. With
many atoms, a large number of molecular orbitals result all
with very similar energies Electrons are able to move easily with very similar energies. Electrons are able to move easily
around different atomic molecular orbitals (Band Model).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Bonding in Solids
Metallic solids.
g
Metals have unique properties: high electrical and thermal conductivity,
malleability
What causes these?
Electrons are arranged around metal atoms in such a way that they
What causes these?
are mobile.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
electron sea model
7.2, 249
Bonding in Solids
I onic solids.
g
Ionic solids contain cations or anions that are held
together by opposing electrostatic forces.
These are strong interactions so melting
temperatures are generally high. p g y g
NaCl Na
+
+ Cl
-
Fp = 801C
Na
NaCl
The stoichiometry of an ionic solid reflects that they
must be electrically charged.
CaF
2
Ca
2+
+ 2F
-
CaF
2
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2
CHEM1020 CHEM1020
Module 1: Lecture 4
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
7.3, 250
Sol ut i ons and Sol ut i ons and
Sol ubi l i t y Sol ubi l i t y
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Wh t F t Aff t S l bilit ? What Factors Affect Solubility?
Solubility: Solubility:
maximum amount of solute that will dissolve in a given amount of
solvent at specific temperature (heterogeneous equilibrium)
Molecular Structure is important Molecular Structure is important
Polar solvent/polar solute or nonpolar solvent/nonpolar solute favoured
eg hexane (C
6
H
14
) is better solvent for grease (C
20
H
14
) than methanol
(CH
3
OH)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Molecule Polarity:
Revision
Molecule Polarity:
Depends on bond polarity and molecular shape ..
nonpolar polar ionic
Blue = positive charge
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p g
Red = negative charge
Chpt 5.5
Try to work out if the following bonds are polar or not? Try to work out if the following bonds are polar or not?
Atom Electronegativity
A. C-C
g y
H 2.1
C 2
B. C-H
C. H-Br
C 2.5
Br 2.8
D. N-H
E. C-O
Cl 3.0
N 3 0
F. O-H
N 3.0
O 3.5
S 2.5
A polar bond has a difference of > 0 4 in electronegativity
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
A polar bond has a difference of > 0.4 in electronegativity
Judging polarity of molecules! Judging polarity of molecules!
The addition of a carbonyl
functional group (-C=O) g p ( )
introduces a dipole.
Electrons become more Electrons become more
localised in one region of
the molecule.
Dipole-dipole interactions
can occur
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Think back to intermolecular interactions! Think back to intermolecular interactions!
Assumed
knowledge from
Senior Chem
Dispersion
Dipole-dipole
Increasing
Strength
Senior Chem
p p
hydrogen bonding (special dipole-dipole case)
Strength
H
2
O CCl
4
Sucrose
P l N l
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Polar Nonpolar
Compare solute-solute and solute-solvent interactions Compare solute-solute and solute-solvent interactions
O
H
O
H
H
H
C C
H
H
O
H
H
H
H H
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Blackman Chapter 10
p 378
Consider 3 solvents:
Water (H
2
O)
Hexane (C
6
H
14
)
Carbon tetrachloride (CCl
4
)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
http://jchemed.chem.wisc.edu/JCESoft/CCA/pirelli/pages/cca2like.html
Solubility of vitamins Solubility of vitamins
Which of these vitamins do you predict to be soluble in water?
H
3
C CH
3
CH3 CH3
CH3
OH
Hydrophobic
Fat soluble: A, D, E, K
CH3
Vitamin A
Like dissolves Like!
O
OH
Like dissolves Like!
Hydrophilic
Water soluble: B, C
O
O
OH
OH
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
ate so ub e , C
HO OH
Vitamin C
Will this molecule dissolve
readily in water? readily in water?
1 No 1. No
2. Yes
3. I dont know!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Solute-solvent interactions must overcome
solute-solute interactions
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p 374
solute-solute interactions
A polar solid will dissolve in water because its molecules A polar solid will dissolve in water because its molecules
are attracted to the polar water molecules:
A nonpolar solid will only dissolve in a nonpolar solvent
b h di i f f bl h because the dispersion forces are of comparable strength
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p 380
Hydration of ions
I i th t l l tti
Hydration of ions
NaCl dissolution
Ions in the crystal lattice can
interact with polar solvents
through formation of ion-dipole
NaCl dissolution
bonds.
In water, each ion is surrounded
by water molecules which form a
hydration shell and the ion is
solvated (aquated)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p 379
Enthalpy diagram for a solid dissolving in a liquid py g g q
Looking Looking
ahead:
enthalpy is a
state state
function!
380
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What we measure is the change represented by the purple arrow
p 380
Chemi cal Thermodynami cs
Chapter 8
Chemi cal Thermodynami cs
The abilit to predict the both the direction and the e tent The ability to predict the both the direction and the extent
of spontaneous chemical and physical change under
particular conditions particular conditions.
Thermochemi st ry
Th t d f h i l d ith h i l ti The study of energy changes involved with chemical reactions
Flanders & Swann:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Flanders & Swann:
http://www.youtube.com/watch?v=KTHiIwxcexI
Wh d i Th h i ? Why are we doing Thermochemistry?
A if i f k f t l d t di t i A unifying framework for not only understanding steam engines,
but for understanding a diverse range of chemical reactions:
Why some reactions are spontaneous
Why gases expand and solutions mix
Why chemical reactions proceed towards equilibrium y p q
Why proteins fold/unfold, form multimers
Refrigeration
.... ....
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What we will investigate:
h l f h l The role of ener gy in chemical reactions
The Fi r st Law of Ther mody nami cs
The Second Law of Ther mody nami cs
How to understand and manipulate thermochemical data to pr edi ct
how ener gy w i l l change in chemical reactions.
How energy changes can pr edi ct spont anei t y .
How to determine the max i mum w or k we can extract from a How to determine the max i mum w or k we can extract from a
reaction.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
ENERGY and Chemical Reactions: ENERGY and Chemical Reactions:
What i s Ener gy ??
1. The capacity to do work. p y
E.g. Lifting an object.
Work done = force x distance
2 The capacity to transfer heat 2. The capacity to transfer heat.
Heat = the pr ocess of t r ansf er of t her mal ener gy between two
bodies or systems at different temperatures We consider heat as bodies or systems at different temperatures. We consider heat as
being unable to do work.
f f f
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
=> Heat is a means of energy transfer, not energy itself!!
Energy: Energy:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
E Ch i Ch i l R ti Energy Changes in Chemical Reactions
Vi t ll ll h i l ti b b l Virtually all chemical reactions absorb or release energy.
In order to understand this, we need to focus on a limited, well-
defined part of universe, called the system. Everything else is called
the surroundings.
The Surroundings +
System = Universe.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
8.2, 284
Types of Systems Types of Systems
O t
Open
System
Matter
Energy
Open system:
can exchange matter and energy with the
surroundings.
Closed
Matter
Closed system:
can exchange only energy with the
Closed
System
Energy
can exchange only energy with the
surroundings.
Isolated
System
Matter
Energy
Isolated system:
can exchange neither matter nor energy
with the surroundings.
The properties of a system at any one time is its State
Energy t t e su ou d gs
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The properties of a system at any one time is its State
CHEM1020 CHEM1020
Module 1: Lecture 5
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Chemical Reactions involve
8.2, 284
Energy Transfer
The system is usually the chemical
reactants and products. The syst em is our
frame of reference.
Energy is transferred to/from a system from/to the sur r oundi ngs.
W k ( ) d H t ( ) th t f d t l i Wor k ( w ) and Heat ( q) are the two fundamental ways in
which energy is transferred to or from a sy st em.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
E l t b t i d b di Energy lost by system = energy gained by surroundings
The First Law of Thermodynamics
Energy cannot be created or destroyed, it
can only be converted from one form to can only be converted from one form to
another.
Where does this energy come from? Where does this energy come from?
=> Internal energy difference between reactants and products.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
8.3, 285
I t l E d Th Fi t L f
The Energy that is transferred comes from the systems internal energy, U.
Internal Energy and The First Law of
Thermodynamics
The internal energy, U is the sum of all the energies e.g. potential,
kinetic for all particles in the system.
We are interested in the change in internal energy during reactions We are interested in the change in internal energy during reactions.
The change in internal energy: AU = U
final
U
initial
If AU is positive system gains energy
If AU is negative system loses energy g y gy
All energy must be released or gained from the surroundings:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
AU
system
= -AU
surroundings
The First Law of Thermodynamics
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l)
The First Law of Thermodynamics
Example: combustion of methane:
Internal Energy
4
(g)
2
(g)
2
(g)
2
( ) p
products have lower
system
CH
4
(g), 2O
2
(g)
U
initial
products have lower
internal energy than
reactants
q
CO
2
(g), 2H
2
O(l)
U
final
In the combustion of methane the system has lower energy at the end
of the reaction energy has been transferred to the surroundings
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
of the reaction energy has been transferred to the surroundings.
=> Exothermic reaction
Exothermic Reactions
Exampl e: Combustion of methane energy g g g g + + + ) ( O 2H ) ( CO ) ( O 2 ) ( CH
2 2 2 4
Exothermic Reactions
Exampl e: Combustion of methane energy g g g g + + + ) ( O 2H ) ( CO ) ( O 2 ) ( CH
2 2 2 4
CH
4
CO
2
Combustion of methane releases energy in form
f h t ( fl f t t
O
2
2
H
2
O
of heat (energy flows from system to
surroundings). => exothermic reaction.
q
Exothermic: products have lower internal energy than
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Exothermic: products have lower internal energy than
reactants
Endothermic Reactions
Other reactions cause energy to flow from surroundings to system:
endot her mi c
Endothermic Reactions
endot her mi c.
) 2NO( energy ) ( O ) ( N
2 2
g g g + + e.g.
CH
N
NO(g)
U
initial
CH
4
O
2
CO
2
N
2
NO
q
q
H
2
O NO
E d h i
N
2
(g), O
2
(g)
U
final
t t h l i t l
Note: energy i s not creat ed or dest royed just transferred from one
Endothermic: reactants have lower internal
energy than productcs
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Note: energy i s not creat ed or dest royed, just transferred from one
place to another
The First Law of Thermodynamics
8.3, 285
The First Law of Thermodynamics
In chemical reactions energy is exchanged with the surroundings
as either heat (q) or work (w).
With respect to chemical reactions, the First Law can be expressed
in terms of w and q.
AU = q + w q
Where q heat added t o system (q< 0 heat removed) Where q = heat added t o system (q< 0 = heat removed)
w = work done on system (w< 0 = work by system)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Important Convention: Important Convention:
Posi t i ve work or heat
i li th t f implies that energy of
system increases.
Negat i ve work or heat
implies that energy of p gy
system decreases.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What is work?
8.3, 285
ff f
What is work ?
There are many different types of work electrical, mechanical
etc. At this stage we are interested in work associated with
contraction and expansion of a gas (pV work).
e.g. If we raise the temperature of a gas the volume increases.
As the gas expands, it pushes back the surroundings, i.e. does As the gas expands, it pushes back the surroundings, i.e. does
work.
w = -p AV w = p
ext
AV
Where AV = V V Where AV = V
final
V
initial
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Rationalisation:
Work = F x d = F x Ah (Change in height)
= p x A x Ah
= pAV
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
E l Exampl e:
A gas expands in volume from 0.1 m
3
to 0.2 m
3
against a
constant pressure of 100 kPa How much work is done? constant pressure of 100 kPa. How much work is done?
A = V p w
ext
Sol ut i on:
( )
m N 10 0 1
m 0.1 m 0.2 m N 10 100
4
3 3 2 3

=

kJ 10
m N 10 0 . 1
4
=
=
Gas does -10 kJ of work.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
(negative sign= work done by system)
What is heat?
8.3, 287
f f f
What is heat ?
Heat = the pr ocess of t r ansf er of t her mal ener gy between
two bodies or systems at different temperatures. We consider
heat as being unable to do work.
Heat is a means of energy transfer, not energy itself!!
We cannot measure heat directly, but we can measure the
temperature change that occurs because heat flows from one temperature change that occurs because heat flows from one
body to another:
q = C AT
Where AT = T
final
T
initial
and C=heat capacity
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
=> Calorimetry: (Blackman p287-293 y our responsibility!)
Internal Energy changes at constant volume
AU = q + w,
Internal Energy changes at constant volume
At constant volume AV is 0, so w = 0 and
AU = q
v
=> AU = heat of reaction at constant volume => AU = heat of reaction at constant volume
Energy as q
Internal energy changes by q
AU
r
can be
measured using a
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
g
bomb calorimeter
Enthalpy
8.3, 284
But, in the majority of cases reactions occur under conditions
Enthalpy.
, j y
of constant pressure (atmospheric).
AU = q + w, and for an expansion: AU q + w, and for an expansion:
AU = q
p
pAV <=> q
p
= AU +pAV
Need a new thermodynamic property that is equivalent to the
heat of reaction at constant pressure ENTHALPY ( H)
H = U + pV
General definition
AH = AU + pAV
Enthalpy changes (e.g.
during a chemical reaction)
at constant pressure
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Enthalpy. py
AU = q
p
pAV Energy as PV work
q
p
= AU + pAV
AH = AU + pAV
Energy as q
p
So: AH = q
Enthalpy changes by q
So: AH q
p
=> AH = heat of reaction at constant pressure
Enthalpy change for a chemical reaction:
AH = H H
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
AH = H
products
- H
reactants
Exothermic Endothermic
8.3, 292
R
y
,

H
P
y
,

H
P
E
n
t
h
a
l
p
y
R
AH > 0 (positive)
AH < 0 (negative)
E
n
t
h
a
l
p
y
Exothermic: Endothermic:
H
products
< H
reactants
, AH < 0 H
products
> H
reactants
, AH > 0
The coffee cup calorimeter
can measure AH
r
directly.
r
y
(specific heat/heat capacity and
calorimetry: Blackman p287-293
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
chemlab.truman.edu
y our responsibility!)
Internal Energy versus Enthalpy.
The general definition for a change in enthalpy:
Internal Energy versus Enthalpy.
The general definition for a change in enthalpy:
AH = AU + A(pV)
For reaction involving only condensed phases expansion is minor For reaction involving only condensed phases, expansion is minor
(i.e. AH AU).
F ti i l i id l For a reaction involving an ideal gas:
AH = AU + A(nRT)
At constant temperature:
AH = AU + RTAn
(Where An = moles product gas moles reactant gas)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
(Where An = moles product gas moles reactant gas)
Internal Energy vs Enthalpy. Internal Energy vs Enthalpy.
C
2
H
5
OH(l) + O
2
(g) CH
3
COOH(l) + H
2
O(l), AH = -492.7 kJ
What is the standard internal energy change
for this reaction at 298K ?
Sol ut i on:
At constant temperature we know that:
AU = AH RTAn
In this case An = 0 mol 1 mol = -1 mol
AU = AH RT(-1 mol) AU AH RT( 1 mol)
= -492.7 x 10
3
J (8.314 JK
-1
mol
-1
x 298 K x -1 mol)
= -490.2 x 10
3
J
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The difference = -2.5 kJ = work done by the system.
Important Enthalpy points. Important Enthalpy points.
1. Ent hapy i s an ex t ensi ve pr oper t y .
If the amounts of reactants doubles, the
enthalpy doubles. Implicit that a quoted AH
applies to a balanced equation applies to a balanced equation.
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g) AH = -802 kJ
2CH
4
(g) + 4O
2
(g) 2CO
2
(g) + 4H
2
O (g) AH = -1604 kJ
This is a Thermodynamically Balanced equation
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
This is a Thermodynamically Balanced equation
(it includes the enthalpy change of the reaction)
Important Enthalpy points. Important Enthalpy points.
2. Enthalpy change of the r ever se r eact i on is of
same magni t ude but opposi t e si gn.
CH (g) + 2O (g) CO (g) + 2H O(g) AH 802 kJ
2H O( ) + CO ( ) CH ( ) + 2O ( ) AH +802 kJ
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g) AH = -802 kJ
2H
2
O(g) + CO
2
(g) CH
4
(g) + 2O
2
(g) AH = +802 kJ
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Important Enthalpy points.
f
Important Enthalpy points.
3. Enthalpy change for a reaction depends on
t he st at e of r eact ant s and pr oduct s.
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(g) AH = -802 kJ
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l) AH = -890 kJ
4
(g)
2
(g)
2
(g)
2
( )
Difference is:
2H O( ) 2H O(l) AH 88 kJ
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2H
2
O(g) 2H
2
O(l) AH = -88 kJ
CHEM1020 CHEM1020
Module 1: Lecture 6
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
State Functions (Property of State).
8.x, xxx
( p y )
When a system changes state, the State Functions
are only dependent on initial and final states. are only dependent on initial and final states.
The change of state is independent of the path
taken. taken.
Work and heat are dependent on the way in which
a change of state has occurred They are not State a change of state has occurred. They are not State
Functions.
Final state Initial state Initial state
10C 10C
Final state Initial state Initial state
heat
freeze
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
http://itl.chem.ufl.edu/2045_s00/lectures/lec_7.html
State Functions (Property of State).
The Final State is independent of the path taken
( p y )
The distance between
Darwin & Dunedin Darwin & Dunedin
remains the same (a
state function) but the
di t t ll d t distance travelled to go
between them is
variable (not a state
function).
C ll If d d t i thi h h d! (X 0)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Corollary: If you do a round trip, nothing has happened! (X = 0)
State Functions (Property of State).
The Final State is independent of the path taken
( p y )
Analogy:
The height difference The height difference
between two points on a
map remains the same (a
t t f ti ) b t th state function) but the
distance travelled to go
between them or the actual
work going up and down are
variable (not a state
function). )
C ll If d d t i thi h h d! (X 0)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Corollary: If you do a round trip, nothing has happened! (X = 0)
State Functions (Property of State).
The Final State is independent of the path taken
( p y )
Analogy:
The height difference The height difference
between two points on a
map remains the same (a
t t f ti ) b t th state function) but the
distance travelled to go
between them or the actual
work going up and down are
variable (not a state
function). )
C ll If d d t i thi h h d! (X 0)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Corollary: If you do a round trip, nothing has happened! (X = 0)
State Functions (Property of State).
The Final State is independent of the path taken
( p y )
Analogy:
The height difference The height difference
between two points on a
map remains the same (a
t t f ti ) b t th state function) but the
distance travelled to go
between them or the actual
work going up and down are
variable (not a state
function). )
C ll If d d t i thi h h d! (X 0)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Corollary: If you do a round trip, nothing has happened! (X = 0)
Why is the concept of State Functions Why is the concept of State Functions
important and useful?
The Fi nal St at e i s i ndependent of t he pat h
t ak en.
The Enthalpy change for a reaction is dependent
only on the energy states of the reactants and only on the energy states of the reactants and
products and is independent of the path or number
of steps taken Hesss Law. of steps taken Hess s Law.
Enthalpy change = H(final) H(initial)
= H(products) H(reactants)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Germain Henri Hess (1802 1850)
Hesss Law.
8.x, xxx
2NO(g) O
2
(g) 2NO(g), O
2
(g)
AH
3
= -112kJ
H
(
k
J
)
2NO
2
(g)
AH = 68kJ = AH + AH AH = 68kJ
2NO
2
(g) AH
2
= 180kJ
N
2
(g), 2O
2
(g)
AH
1
= 68kJ = AH
2
+ AH
3
AH
1
= 68kJ
N
2
(g), 2O
2
(g)
Enthalpy change = H(final) H(initial) Enthalpy change = H(final) H(initial)
= H(products) H(reactants)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
(p ) ( )
Hesss Law
Standard Enthalpy of Formation
Hess s Law
Standard Enthalpy of Formation.
Can use Hess s Law t o cal cul at e AH f or many r eact i ons
usi ng t abul at ed ent hal pi es.
Important tabulated values are St andard Ent halpies ( or heat s)
of Format ion.
Ent hal py of For mat i on (AH
f
): enthalpy change associated
with formation of 1 mole of a substance from its elements (C +
O CO) O
2
CO)
But: depends on conditions.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Standard Enthalpy of Formation.
Depends on state (s, l, g), temperature and
py
pressure.
We define a st andar d st at e the most stable form We define a st andar d st at e the most stable form
at 1 atm and temperature of interest (usually 298K).
For compounds: Gases 1 atm
Liquids pure
l Solutions: 1M
E g the standard state for water is liquid not ice E.g. the standard state for water is liquid, not ice.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Standard Enthalpy of Formation.
Standard enthalpy of formation (AH

f
)
py
Enthalpy change that results when 1 mol e of a compound is
formed from its elements, with all substances in standard ,
states
6C(s) + 6H
2
(g) + 3O
2
(g) C
6
H
12
O
6
(s)
Not:
6CO
2
(g) + 6H
2
O(l) C
6
H
12
O
6
(s) + 6O
2
(g)
The reaction does not have to be real The reaction does not have to be real.
H
2
(g) + O
2
(g) H
2
O
2
(l), will not happen.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Standard Enthalpy of Formation. py
The standard enthalpy of formation for an element
in its standard state is ZERO.
Elements are not formed, they justare!
O
2
(g) O
2
(g) AH

f
= 0
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
A Thermochemical Table A Thermochemical Table
Note: AH

f
is in kJ/mol
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Blackman, Appendix A, pageA-1 to A-3
How do we use it?
We can determine AH directly via constant pressure We can determine AH
r
directly via constant pressure
calorimetry.
B t t di ti i d t iti ! N t l But: tedious, time consuming and not very exciting! Not always
feasible.
We can use t her mody nami c t abl es t o det er mi ne AH
r x n
,
w i t hout ent er i ng a l abor at or y .
If a reaction is carried out in a series of steps, the enthalpy
change will be equal to the sum of the enthalpy changes for the change will be equal to the sum of the enthalpy changes for the
individual steps.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
This means we can manipulate This means we can manipulate
chemical reactions.
1. Take reactants apart to their constituent elements
2. Form products from the elements
Reactants Products
AH
rxn
E(AH

f
(r))
E(AH

f
(p))
Constituent Elements
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
For a general (hypothetical) reaction: g ( yp )
aA + bB cC + dD aA + bB cC + dD
Then:
AH

= [cAH

(C) + dAH

(D)] [aAH

(A) + bAH

(B)] AH
rxn
= [cAH
f
(C) + dAH
f
(D)] - [aAH
f
(A) + bAH
f
(B)]
AH

rxn
= EnAH

f
(products) - EnAH

f
(reactants)
Where n = coefficients in the balanced equation.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example: Example:
Calculate the standard enthalpy change Calculate the standard enthalpy change
for combustion of ammonia in air:
4NH (g) + 7O (g) 4NO (g) + 6H O(l) 4NH
3
(g) + 7O
2
(g) 4NO
2
(g) + 6H
2
O(l)
AH

rxn
= [cAH

f
(C) + dAH

f
(D)] - [aAH

f
(A) + bAH

f
(B)]
AH

rxn
= [4AH

f
(NO
2
(g)) + 6AH

f
(H
2
O(l))] - [4AH

f
(NH
3
(g)) + 7AH

f
(O
2
(g))]
= 4 33.2 + 6 -285.8 4 -46.1 0
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
= -1396 kJ
Is this a sensible answer?
For examples of how to use Hesss Law see Worked For examples of how to use Hess s Law see Worked
Example 8.9, page 300 of Blackman.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Again: important things to remember Again: important things to remember
when manipulating reactions.
1. If you reverse a reaction be sure to change the sign on AH.
C O( ) H ( ) C ( ) H O(l) H 130 6 kJ CuO(s) + H
2
(g) Cu(s) + H
2
O(l) AH = -130.6 kJ
Cu(s) + H
2
O(l) CuO(s) + H
2
(g) AH = +130.6 kJ
[You will come across this concept again in Module 4 (electrochemistry)]
2. If you multiply by a coefficient, multiply AH by the same
coefficient (AH is ext ensive).
CuO(s) + H
2
(g) Cu(s) + H
2
O(l) AH = -130.6 kJ
2CuO(s) + 2H (g) 2Cu(s) + 2H O(l) AH = -261 2 kJ
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2CuO(s) + 2H
2
(g) 2Cu(s) + 2H
2
O(l) AH = -261.2 kJ
Example: p
Two forms of carbon are graphite and
diamond Given the following data diamond. Given the following data,
calculate AH for the conversion of
graphite to diamond.
www.encarta.msn.com
C(graphit e) + O
2
(g) CO
2
(g) AH = -394 kJ
C(diamond) +O
2
(g) CO
2
(g) AH = -396 kJ
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
E l Example:
Solution:
Reverse the second reaction and sum the two
C(graphit e) + O
2
(g) CO
2
(g) AH = -394 kJ
CO
2
(g) C(diamond) +O
2
(g) AH = +396 kJ
C(graphit e) C(diamond) AH = +2 kJ C(graphit e) C(diamond) AH +2 kJ
Thus 2 kJ of energy is required to convert 1 mol of Thus 2 kJ of energy is required to convert 1 mol of
graphite to diamond (endothermic process)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example: p
Ethanol in petrol
With petrol approaching $2/litre it is cheaper to buy ethanol
blended fuel. If petrol contains 10% (by mass) ethanol, what blended fuel. If petrol contains 10% (by mass) ethanol, what
effect does it have on fuel efficiency?
1
l kJ 278 )] ( OH H C [ A l H Relevant data:
1
18 8
1
5 2
mol kJ 251 )] ( H C [
mol kJ 278 )] ( OH H C [

= A
= A
l H
l H
f
f
1
2
1
2
mol kJ 286 )] ( O H [
mol kJ 5 . 393 )] ( CO [

= A
= A
l H
g H
f
f
How much heat is produced by burning one gram of ethanol,
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p y g g ,
compared to one gram of octane?
Example:
The combustion of octane:
p
Ethanol in petrol
On a mass basis:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example: Ethanol in petrol
The combustion of ethanol:
On a mass basis:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
RACQ - Blends of up to 10 percent ethanol in petrol (E10) have been declared suitable for use in most
but not all post-1986 petrol-engine vehicles in Australia. E10 increases fuel consumption between 2.6
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
and 5 per cent relative to unblended petrol.
So: its cheaper and potentially more environmentally friendly but you use more of it..
Enthalpy and Phase Changes.
7.3, 251
Heat is also required for a phase change (Module 2).
This is the Enthalpy of the phase change The magnitude is
py g
This is the Enthalpy of the phase change. The magnitude is
dependent on the strength of the intermolecular forces.
solid liquid (heat in) A
fus
H
liquid gas A
vap
H
Critical
point
p
solid gas A
sub
H
Solid
Liquid
e
s
s
u
r
e

(
a
t
m
)
liquid solid (heat out) A
solid
H = -A
fus
H
gas liquid A
d i
H = -A H
Gas
P
r
e
Triple
point
gas liquid A
condensation
H = -A
vap
H
gas solid A
deposition
H = -A
sub
H
Temperature (C)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Note: you may want to go back and review this slide and intermolecular forces, once you have encountered phase
changes.
What you should be able to do at this stage:
1. Define and explain the First Law of Thermodynamics and its relation to
chemical reactions. chemical reactions.
2. Explain what is meant by the terms System, Surroundings and the Universe
with respect to chemical reactions.
3. Explain how energy is transferred in chemical reactions.
4. Explain what Internal energy (U) and Enthalpy (H) are and how they are
related related.
5. How is work defined in chemical reactions (with relation to enthalpy)?
6 Be able to identify and balance a thermodynamic equation 6. Be able to identify and balance a thermodynamic equation.
7. Explain what a State Function is and how Hesss law exploits it.
8 Explain what is meant by Standard Enthalpy of Formation 8. Explain what is meant by Standard Enthalpy of Formation.
9. Use thermochemical data to predict the enthalpy change for a reaction.
10 Explain what an Exothermic reaction and an Endothermic reaction mean in
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
10.Explain what an Exothermic reaction and an Endothermic reaction mean in
relation to enthalpy changes.
CHEM1020 CHEM1020
Module 1: Lecture 7
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2: Thermochemist ry
What we will investigate:
2: Thermochemist ry.
What we will investigate:
The role of energy in chemical reactions
\
First Law of Thermodynamics
\
How to understand and manipulate
thermochemical data to predict how energy \ p gy
will change in chemical reactions.
\
How energy changes can predict spontaneity.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What determines whether or not a
Enthalpy?
process will be spontaneous?
Enthalpy?
We observe that many exothermic reactions are
i d d t indeed spontaneous.
H
+
(aq) + OH
-
(aq) H O(l) AH = -56 2 kJ H
+
(aq) + OH (aq) H
2
O(l) AH = -56.2 kJ
But: so are some endothermic reactions But: so are some endothermic reactions.
H
2
O(s) H
2
O(l) AH = 6 01 kJ (25C) H
2
O(s) H
2
O(l) AH = 6.01 kJ (25 C)
L l k
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Lets look at some spontaneous processes
A Spontaneous Process: p
A hot object cooling
Not spont aneous
Hot Cold
spont aneous
Hotter
A h t bj t l l h t bj t ill t l A hot object always cools, a hot object will never spontaneously
absorb heat from colder surroundings to heat up.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
A Spontaneous Process: p
A hot object cooling
Hot Cold
A nat ural change
What is different between the hot cube and the cold cube? What is different between the hot cube and the cold cube?
ENERGY
the hot cube is characterised by molecules having
greater kinetic energy (and therefore a higher greater kinetic energy (and therefore a higher
temperature).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Think: where has this energy gone with cooling?
A process is said to be A process is said to be
SPONTANEOUS
if it ith t if it occurs without
outside intervention
Thermodynamics tell us about the direction
f N t th d f th of a process Not the speed of the process
I i i l di d h ld e.g. In principle a diamond should
change spontaneously to graphite
H V l - However: Very slow process
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Spontaneous (adj) 1 proceeding from natural Spontaneous (adj) 1. proceeding from natural
feeling or native tendency without external
constraint constraint.
There is nothing in the definition of spontaneous
that describes how FAST the process is.
Kinet ics tells us how fast a reaction is [Module 4] Kinet ics tells us how fast a reaction is [Module 4].
Thermodynamics tells us if it will proceed at all.
Remember this!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Spontaneous Processes Spontaneous Processes
e.g.
A Ball rolls down a hill never spontaneously up a hill
A gas fills a container uniformly
Heat flow always from hot to cold object never the reverse
At temperatures below 0
o
C water spontaneously freezes at temperatures At temperatures below 0 C water spontaneously freezes, at temperatures
> 0
o
C ice spontaneously melts
WHY?
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Is this due to an exothermic process? Is this due to an exothermic process?
No: The melting of ice occurs spontaneously g p y
above 0
o
C Endothermic process
Looking ahead: The driving force for
spontaneity is an increase in the
entropy of the universe
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
entropy of the universe
S h t i E t ?
8.4, 304
E t i f E di t ib ti
So what is Entropy?
Entropy is a measure of Energy distribution
N b f t Number of arrangements
available to a system
Nature spontaneously
proceeds towards states
that have the highest
probability of existing.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Entropy is a measure of Energy distribution
8.4, 305
High-energy molecules Low-energy molecules
Lets bring 3 high-energy molecules in contact with 3 low-
energy molecules => What is going to happen??
Entropy is a measure of Energy distribution
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Entropy is a measure of Energy distribution
8.4, 305
High-energy molecules Low-energy molecules
Lets bring 3 high-energy molecules in contact with 3 low-
energy molecules => What is going to happen??
Entropy is a measure of Energy distribution
Number of arrangements available to a system
0 energy units transferred 1 energy unit transferred 2 energy units transferred 3 energy units transferred
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Nature spontaneously proceeds towards states that have the highest probability of existing.
Entropy is a measure of Energy distribution
8.4, 305
High-energy molecules Low-energy molecules
Lets bring 3 high-energy molecules in contact with 3 low-
energy molecules => What is going to happen??
Entropy is a measure of Energy distribution
Macrostates
Number of arrangements available to a system
0 energy units transferred 1 energy unit transferred 2 energy units transferred 3 energy units transferred
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Nature spontaneously proceeds towards states that have the highest probability of existing.
Entropy is a measure of Energy distribution
8.4, 305
High-energy molecules Low-energy molecules
Lets bring 3 high-energy molecules in contact with 3 low-
energy molecules => What is going to happen??
Entropy is a measure of Energy distribution
Macrostates
Microstates Microstates
Microstates = Number of arrangements available to a system
0 energy units transferred 1 energy unit transferred 2 energy units transferred 3 energy units transferred
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Nature spontaneously proceeds towards macrostates that have the highest probability of
existing = the highest number of microstates.
Lets think in terms of Probability
8.4, 305
Lets think in terms of Probability
0 energy units transferred 1 energy unit transferred 2 energy units transferred 3 energy units transferred 0 energy units transferred 1 energy unit transferred 2 energy units transferred 3 energy units transferred
p=5% p=45% p=45% p=5%
Which do you think is the most probable state?
Spontaneous processes proceed from macrostates of low probability
to macrostates of higher probability
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Spont aneous pr ocesses t end t o di sper se ener gy .
This is important:
8.4, 306
p
Spont aneous pr ocesses t end t o di sper se ener gy .
We can now introduce a quantity that is a measure f or how
di spersed energy i s it is called ent ropy.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
di spersed energy i s it is called ent ropy.
Entropy and volume
8.4, 307
Entropy and volume
c
e
s
s
i
b
l
e

v
e
l
s
m
b
e
r

o
f

a
c
c
e
n
e
r
g
y

l
e
v
N
u
m
e
The distribution of an identical amount of energy is greater in the larger volume.
This is important:
The distribution of ener gy not of mol ecul es is the important
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The distribution of ener gy , not of mol ecul es is the important
factor when considering entropy!!
Second Law of Thermodynamics
8.4, 309
y
In any spontaneous process there is always an In any spontaneous process there is always an
increase in the Entropy of the Universe.
AS
uni verse
= AS
sys
+ AS
surr
If AS
univ
= positive (>0) Entropy of the universe increases.
If S i ( 0) i i h If AS
univ
= negative (<0) process is spontaneous in the
opposite direction
If AS
univ
= 0 equilibrium has been reached.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
And a second formulation of
8.4, 309
And a second formulation of
The Second Law of Ther mody nami cs. y
Nat ur e spont aneousl y pr oceeds
t ow ar d t he st at es t hat al l ow gr eat er t ow ar d t he st at es t hat al l ow gr eat er
di f f usi on of ener gy and t hus hav e
hi gher pr obabi l i t y of ex i st i ng hi gher pr obabi l i t y of ex i st i ng
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Our t w o Law s of Ther mody nami cs.
Ener gy i s conser v ed. Ener gy i s conser v ed.
Ent r opy i n max i mi sed.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
We are interested in Entropy changes.
Entropy is a state function, so
We are interested in Entropy changes.
AS = S
final
S
initial
Similarly to Enthalpy, we have to take into account the system
and the surroundings and the surroundings.
Where the surroundings + system = universe.
AS
univ
= entropy change in the universe
AS = entropy change in the system AS
sys
entropy change in the system
AS
surr
= entropy change in the surroundings
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Interplay of AS
sys
and AS
surr
determines the
S S S 0
p y
sys surr
sign of AS
univ
AS
universe
= AS
system
+ AS
surr
> 0
Zumdahl, 2006
Note: one of the entropy changes may be negative, but sum must be positive.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
If AS
univ
< 0, process will not be spontaneous as writ t en, but is spontaneous in the
reverse direction.
Entropy changes and real life. py g
How do we end up with
complex systems that have
no apparent entropy i.e. pp py
how do we end up with a
system having localised
energy?
AS
universe
= AS
system
+ AS
surr
> 0
energy?
Large and positive
Negative
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
A thermodynamic caveat.
Transferring the Second Law to Life is not a good idea!
y
g g
Remember these laws were essentially developed for chemical
reactions (steam trains and reactions in test tubes) where the
Universe = Test Tubes + Water Bath Universe = Test Tubes + Water Bath..
i.e. You can ask yourself if life violates the Second Law but
dont expect to prove/disprove it with Chem1020 alone! don t expect to prove/disprove it with Chem1020 alone!
D. R. Brooks and E. O. Wiley.
Evolution as Entropy. SS&H, QH371.B69 Evolution as Entropy. SS&H, QH371.B69
Thorne K. S. et al.
Black Holes The membrane paradigm PS&E
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Black Holes The membrane paradigm. PS&E
QB843,B55.B59
A closer look at entropy
8.4, 309
A closer look at entropy
To determine spontaneity (=AS
univ
), we need to know
AS
sys
and AS
surr
.
How does the entropy of the system and the surroundings
h d i ? change during a process?
The only way we can exchange energy between system and
the surroundings is via work (w) or heat (q).
=> We need to find a t her mody mani c definition of entropy,
and this definition will contain heat f l ow as the important
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
and this definition will contain heat f l ow as the important
factor.
The thermodynamic definition of The thermodynamic definition of
ENTROPY is:
q
r
T
S = J K
-1
T
(So heat flow is the important factor in determining entropy.)
But w hy ???! But w hy ???!
It all started with steam engines
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Optional reading: Carnot Heat Engines
The Car not Cy cl e
In the days of steam engines
y
http://commons.wikimedia.org/wiki/File:Tower_bridge_steam_engine.jpg
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
http://cache-media.britannica.com/eb-media/11/71511-004-321E1907.jpg http://www.todayinsci.com/H/Hornblower_Jonathan/HornblowerJonathanPatent1298.htm
The Car not Cy cl e y
Cy cl i c pr ocess w i t h 4 st eps:
1. Isothermal expansion at T
1
(hot) p
1
( )
2. Adiabatic expansion (T
1
T
2
3. Isothermal compression at T
2
(cold)
4. Adiabatic compression (T
2
T
1
)
We can l ook at Wor k , Heat and ef f i ci ency ( q) f or t hi s ci r cul ar pr ocess:
= Model for any cyclic process!!
, y ( q) p
q
1
=-w
tot
+ -q
2
-w
tot
= q
1
+q
2
=> q = -w
tot
/q
1
= (q
1
+q
2
)/q
1
T
1
> q w
tot
/q
1
(q
1
+q
2
)/q
1
Also: q = (T
1
-T
2
)/T
1
( der i vat i on: RED BOX CHALLENGE! )
system
q
1
-w
tot
q =(q
1
+q
2
)/q
1
= (T
1
-T
2
)/T
1
1+ q
2
/q
1
= 1 T
2
/T
1
=> q
1
/T
1
+ q
2
/T
2
= 0 for this process
T
2
-q
2
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
= > q/ T = st at e f unct i on! ! = > Ent r opy ! ! !
We can define a standard entropy (S) py ( )
Notice enthalpy as AH py
But entropy as just S
Wh ? Why?
To understand that we need to focus on
t her mody nami c ent r opy = Entropy as it relates to
the occupancy and probability of energy levels with
l i h l i h
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
relation to thermal energy i.e. heat.
Standard entropy (S) and thermodynamic Standard entropy (S ) and thermodynamic
definition of Entropy:
The thermodynamic definition of ENTROPY is:
q
r
S = J K
-1
T
S = J K
1
At absolute zero T=0 so heat cannot be transferred
so S 0 (theoretically) so S = 0 (theoretically)
We can then determine S as the temperature
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
We can then determine S as the temperature
increases until we arrive at S (298 K, 1 atm)
8.4, 308
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Thi rd Law of Thermodynami cs The Thi rd Law of Thermodynami cs
Consider a perfect crystal of HCl at 0 K:
Entropy of such a crystal is
zero since there is only one
+ - + - + - + - + -
zero, since there is only one
way to achieve perfect
order
+ -
+
+ - + -
+ + +
+ - + -
+
Third Law of Thermodynamics: The entropy of a perfect
+ - + - + - + - + -
Third Law of Thermodynamics: The entropy of a perfect
crystal at 0 K is zero.
Disorder appears as crystal is warmed, leading to increase
in entropy. Values of S are absolute entropies (cf H, U,
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
etc)
CHEM1020 CHEM1020
Module 1: Lecture 8
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Reaction Entropy from Standard Entropies
Ex ampl e: Calculate AS for the synthesis of ammonia from
H d N
Reaction Entropy from Standard Entropies
H
2
and N
2
:
N
2
(g) + 3H
2
(g) 2NH
3
(g)
AS
rxn
= 2 S(NH
3
) [S(N
2
) + 3 S(H
2
)]
= 2 * 192.5 [191.6 + 3 * 130.7]
= -198.7 JK
-1
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Not e: S for elements is not equal to zero
198.7 JK
AS
rxn
< 0 for the Haber process: N
2
(g) + 3H
2
(g) 2NH
3
(g)
G t E t Greater Entropy
Less Entropy
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Reduction of ways in which energy can be distributed
Rules for Entropy Changes
(1) S for elements is not equal to zero
py g
( ) q
(2) Reactions that consume or generate gases can have
predictable entropy changes predictable entropy changes.
Could predict that AS for Haber reaction < 0, since there
are 4 moles of gas on the left and 2 on the right.
N
2
(g) + 3H
2
(g) 2NH
3
(g)
I
2
(g) 2I(g) AS
0
> 0
4Fe(s) + 3O
2
(g) 2Fe
2
O
3
(s) AS
0
< 0
Ex ampl e: Al
2
O
3
(s) + 3H
2
(g) 2Al(s) + 3H
2
O(g)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2 3 2 2
1. Prediction: the problem of rust 1. Prediction: the problem of rust
+
4 mol Fe (s)
3 mol O
2
(g)
2
(g)
2 mol Fe
2
O
3
(s)
AS
sys
< 0
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
AS
sys
0
2. Prediction: Complex molecules 2. Prediction: Complex molecules
Al
2
O
3
(s) + 3H
2
(g) 2Al(s) + 3H
2
O(g)
As 3 mol hydrogen forms 3 mol water vapour one
would assume AS to be zero (no change in number of
gas molecules).
However, AS is large and positive, why?
Due t o f or mat i on of a mor e compl ex
mol ecul e.
Remember? The distribution of energy, not of mol ecul es is the important
The H
2
O molecule can vibrate and rotate in several ways.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
gy p
factor when considering entropy!!
Liquid H
2
O has a relatively low
entropy. Why?
Remember intermolecular forces?
Just another manifestation of the
network of hydrogen bonding network of hydrogen bonding.
High BP, Low entropy H-bonds
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Rules for Entropy Changes
The entropy for gas is larger than for liquid which is larger than
py g
py g g q g
for a solid
The more complex the molecule, the higher the entropy p , g py
Forming a solution from a molecular solid yields an increase in
entropy entropy
Forming a solution from a salt can cause either an increase or
decrease in entropy decrease in entropy
Pressure and Temperature affect entropy
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Pressure and Entropy
Which has the higher entropy?
N
2
gas at 1 atm or N
2
gas at 1x10
-2
atm?
py
N
2
gas at 1 atm or N
2
gas at 1x10 atm?
pV = nRT
One mole of N
2
gas at 1x10
-2
atm has a volume 100 times
that of one mole of N
2
gas at 1 atm. Thus, N
2
gas at 1x10
-2
2
g ,
2
g
atm has the higher entropy (particle in a box)
1x10
-2
atm
>>
1 atm
S
low pressure
> S
high pressure
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Temperature and Entropy
Why is temperature so important?
p py
y

l
e
v
e
l
s
e

e
n
e
r
g
y
A
c
c
e
s
s
i
b
l
Absolute zero
(BEC)
A
Temp 1 Temp 2
A change in temperature can make a huge difference
to accessible energy levels and thus the distribution
of ene g in those le els
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
of energy in those levels.
What you should be able to do at this y
stage:
1 D fi h t i t b t ti 1. Define what is meant by a spontaneous reaction.
2. Define the Second Law of Thermodynamics.
3. Explain what is meant by entropy.
4. Describe how entropy changes for a spontaneous reaction.
5. Predict entropy changes based on analysis of a 5. Predict entropy changes based on analysis of a
thermodynamically balanced equation (e.g. formation of gases,
higher complexity molecules).
6. Use thermochemical data to predict the entropy change for a
system.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
7. Describe how temperature affects entropy.
Interplay of AS
sys
and AS
surr
determines Interplay of AS
sys
and AS
surr
determines
the sign of AS
univ
AS
universe
= AS
system
+ AS
surr
> 0
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Zumdahl, 2006
We can determine the system entropy
8.4, 309
change, but what about entropy changes in
the surroundings?
To determine spontaneity, we need to know AS
sys
+ AS
surr
. How does the entropy of the
surroundings change during a process?
The only way we can exchange energy with the
surroundings is via work (w) or heat (q) surroundings is via work (w) or heat (q).
The thermodymanic definition of entropy is:
q / T
so heat flow is the important factor
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
so heat flow is the important factor.
Heat flow to the surroundings - S
surr
?
8.4, 309
Th t h i th di i d t
Heat flow to the surroundings S
surr
?
The entropy change in the surroundings is due to
heat transfer from the system (conservation of
energy) energy).
S
surr
= q/T
Therefore spontaneity is often dependent on
E d h i i b temperature. Eg an endothermic reaction may be
spontaneous at high temperature, but not at low.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Remember Enthalpy?
Recal l :
Heat flow (q) = AH (at constant p)
Remember Enthalpy?
Heat flow (q) AH (at constant p)
+ si gn: endot her mi c ( i nt o t he sy st em)
- sign: exothermic (out of the system)
AH
So:
At constant temperature and
pressure.
AS
surr
=
-AH
sys
T
+ sign: exothermic
- si gn: endot her mi c
AS
universe
= AS
system
+ AS
surr
> 0
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
universe system surr
1 The sign of AS depends on direction of heat 1. The sign of AS
surr
depends on direction of heat
flow.
2. The magnitude of AS
surr
depends on
temperature
Driving force
provided by
=
Magnitude of
the entropy
=
Quantity of heat (J)
energy flow
(heat)
py
change of the
surroundings
Temperature (K)
=
Quantity of heat (J)
Temperature (K)
+
AS
surr
Exothermic
Temperature (K)
=
Quantity of heat (J)
- AS
surr
Endothermic
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Temperature (K)
surr
Heat flow (constant p) = AH Heat flow (constant p) AH
=
AH
-
AS
surr
-ve sign because enthalpy with respect to system
T
AS
surr
ve sign because enthalpy with respect to system
1. The sign of AS
surr
depends on direction of heat flow.
2. The magnitude of AS
surr
depends on temperature and
magnitude of enthalpy
As T increases, AS
surr
decreases
The impact of the transfer of a given quantity of energy as heat to
or from the surroundings will be greater at lower temperatures
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The problem of rust
4Fe(s) + 3O
2
(g) 2Fe
2
O
3
(s) AS
0
< 0 (prediction)
p
4 mol Fe
But experimentally, rusting is spontaneous
AS =
-AH
sys
+
AS
surr
=
T
AH = 1648 4 kJ so at 298K
3 mol O
2
AH = -1648.4 kJ, so at 298K
AS
surr
= -(-1648.4 x 10
3
J)/298K = +5529 J/K
AS
sys
= -549.4 J/K
2 mol Fe
2
O
3
AS
univ
= -549.4 + 5529
= 4980 J/K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Gi bbs Fr ee Ener gy
8.2, 283
AS
univ
= AS
sys
+ AS
surr
.
But its inconvenient as a measure of spontaneity, since required
to know about system and surroundings.
We want a simple thermodynamic function related to
spontaneity which only requires knowledge of system.
Thanks to J. Williard Gibbs we do:
The Gi bbs f unct i on ( G)
In 1876 Gibbs published the first part of the work for which he is
most famous On the Equilibrium of Heterogeneous Substances
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
most famous On the Equilibrium of Heterogeneous Substances,
publishing the second part of this work in 1878.
Converting the general equation to one involving only
AS
uni verse
= AS
syst em
+ AS
surr
g g q g y
system variables.
uni verse syst em surr
AH
sys
T
AS
uni verse
= AS
syst em
-
T
TAS
uni verse
= AH
syst em
- TAS
syst em
AG= AH - TAS
Thi s i s t he 2
nd
equat i on
t o remember! ! !
AG AH TAS
AG i s t he Gi bbs Funct i on of a process at const ant pr essur e and
t o remember! ! !
t emper at ur e
Just a more conveni ent way of det ermi ni ng i f a process i s
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Just a more conveni ent way of det ermi ni ng i f a process i s
spont aneousbut i t i s much more usef ul t han t hat .
Why is this useful?
8.2, 284
W y s t s use ul?
If the process is spontaneous:
AS
uni verse
= AS
syst em
+ AS
surr
> 0
AH
sys
T
AS
uni verse
= AS
syst em
- > 0
T
TAS
uni verse
= AH
syst em
TAS
syst em
< 0
AG= AH TAS < 0
AG w i l l be negat i v e f or a spont aneous pr ocess!
( at const ant p and T)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
( at const ant p and T)
Hence a process will be spontaneous if Hence a process will be spontaneous if
AH
sys
- TAS
sys
< 0
sys sys
i.e. if AG < 0 process is spontaneous
if AG > 0 reverse process is spontaneous p p
if AG = 0 system is at equilibrium
Two f unct i ons t hat can predi ct spont anei t y:
G: T p constant (+ reaction mixture constant) G: T, p constant (+ reaction mixture constant)
S
univ
: all processes
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Exampl e: Why does ice melt at 10C, but not Exampl e: Why does ice melt at 10 C, but not
at -10C?
H
2
O(s) H
2
O(l) AH = 6.01 kJ
t > 0C t > 0C
t < 0C
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
T T AH AS AS
s rr
AS
niv
AG
kJ 03 . 6 ) ( O H ) ( O H
0
2 2
= A H l s
T T AH AS AS
surr
AS
univ
AG
C K kJ J K
-1
J K
-1
J K
-1
J mol
-1
-10 263 6.03 22.1 -22.9 -0.8 +220
0 273 6 03 22 1 -22 1 0 0 0 273 6.03 22.1 22.1 0 0
+10 283 6.03 22.1 -21.3 +0.8 -220
Thus at +10C ice melts spontaneously but at 10C Thus at +10C, ice melts spontaneously, but at -10C,
water freezes spontaneously.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
8.5, 314
S f th ff t f th i f AH Summary of the effects of the signs of AH
and AS on spontaneity
Only when the negative
l f AH i l th value of AH is larger than
the negative value of TAS
will AG be negative will AG be negative
H
2
O(l) H
2
O(s)
This is an exothermic change
i d b d accompanied by a decrease
in entropy so is spontaneous
only at low temps (below 0
o
C)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
only at low temps (below 0 C)
Entropy term does not always oppose enthalpy term
8.5, 314
Various combinations are possible:
Entropy term does not always oppose enthalpy term.
AH AS AG Example
p
____________________________________________________________
+ + Spont. at high temp. CaCO
3
(s)
Reverse spont at low temp C O( ) + CO ( ) Reverse spont. at low temp. CaO(s) + CO
2
(g)
Spont. at low temp, reverse CaO(s) + CO
2
(g)
spont. at high temp. CaCO
3
(s)
+ AG always +. 3O
2
(g) 2O
3
(g)
Reverse rxn spont. at all temps.
+ AG always . 2O
3
(g) 3O
2
(g) AG always . 2O
3
(g) 3O
2
(g)
Spont. at all temps.
______________________________________________________________________________________________________________
AG= AH TAS (AG negative for spontaneity)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
AG= AH TAS (AG negative for spontaneity)
Ex ampl e: Ex ampl e:
At what temperature would processes with the
following values of AH and AS be at equilibrium? following values of AH and AS be at equilibrium?
a) AH = +10 kJ; AS = -220 J K
-1
b) AH = +10 kJ; AS = +184 J K
-1
At equilibrium we know AG = 0, so given the data we
need to solve:
AG = AH - TAS
need to solve:
for the temperature T.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Sol ut i on:
a)AG = 10 000 J + 220 J K
-1
x T = 0
thi t b t t t - this cannot be zero at any temperature
This process has AG +ve at all temperatures.
b) AG = 10 000 J 184 J K
-1
x T = 0 b) AG = 10 000 J - 184 J K
1
x T = 0
- this equals zero at T = 54.3 K.
Below 54.3 K, AG is > 0 (not spontaneous)
Above 54 3 K AG is < 0 (spontaneous) Above 54.3 K, AG is < 0 (spontaneous)
i.e. we can determine the temperature at which a
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p
non-spontaneous reaction becomes spontaneous.
CHEM1020 CHEM1020
Module 1: Lecture 9
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
St andard Gi bbs Free Energy Changes
8.5, 314
gy g
As for AH, we define AG (standard Gibbs Free Energy
change) as the change for a reaction carried out under
standard state conditions, with all reactants and products in
standard states standard states.
Also use standard free energies of formation (AG
f
)
. f
For aA + bB cC + dD,
AG

rxn
= [cAG

f
(C) + dAG

f
(D)] - [aAG

f
(A) + bAG

f
(B)]
Exactly analogous to use of AH
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Standard Free Energy of Formation gy
AG
f

AG
f

is the change in the Gibbs Free Energy when one mole of a


substance is created from its constituent elements, with all species
being in their standard states being in their standard states.
Like AH
f

, AG
f

has units of kJ mol


-1
.
Like AH
f

for an element in its standard state, AG


f

is defined to be zero.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Standard Free Energy of Formation The Standard Free Energy of Formation
AG
f

AG

cannot be measured directly by


means of any instrumentation
AG

can be calculated from other


d titi measured quantities
H

b d i d b i AH

can be determined by measuring


heat flow in a calorimeter
S

can be determined experimentally


School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
8.5, 314 - 315
Three ways to determine AG

:
1. AG

rxn
= n
p
AG

f,prod
n
r
AG

f,react
2. AG

= AH

TAS

3. Reaction Manipulation (calculating from other rns.)


L th ! Learn these ways!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Methods for Calculating AG

(1)
2CH
3
OH(g) + 3O
2
(g) 2CO
2
(g) + 4H
2
O(g)
g ( )
AG
f
-163 kJ/mol 0 kJ/mol -394 kJ/mol -229 kJ/mol
AG = 2AG
f

(CO
2
(g)) + 4AG
f

(H
2
O(g)) (2AG
f

(CH
3
OH(g)) - 3AG
f

(O
2
(g))
= 2mol(-394 kJ/mol) + 4mol(-229 kJ/mol)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2mol(-163 kJ/mol) 3mol(0 kJ/mol) = -1378 kJ
Methods for Calculating AG

(2)
AG

= AH

- T AS

g ( )
Consider the reaction
2SO
2
(g) + O
2
(g) 2SO
3
(g)
carried out at 25C and 1 atm. Calculate AH, AS, and AG using the
following data:
Substance AH (kJ/mol) S (J/K mol)

f
SO
2
(g) -297 248
SO
3
(g) -396 257
O
2
(g) 0 205
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
2 2
)) ( (O f )) ( (SO f (g))
3
(SO f
2 2
A A A = A
g g
H H H H

kJ 594 kJ 792
0 kJ/mol) 297 ( mol 2 kJ/mol) 396 ( mol 2
+ =
=
kJ 198 =
2 2 ) ( O ) ( SO ) ( SO
2 2 3
= A g g g S S S S

J/K 205 - J/K 496 - J/K 514
mol) J/K mol(205 1 mol) (248J/K mol 2 mol) J/K (257 mol 2
=
=
J/K 187 -
J/K 205 J/K 496 J/K 514
=
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
J | |
A A = A

S T H G
K
J
187 ) K 298 ( J 000 , 198
|
.
|

\
|
=
kJ 142
J 700 , 55 J 000 , 198 + =
kJ 142 =
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Methods for Calculating AG

(3)
The Free Energy is a State Function so we can manipulate any
number of reactions (Hesss Law)
g ( )
C
diamond
(s) C
graphite
(s)
number of reactions (Hess s Law)
C
diamond
(s) + O
2
(g) CO
2
(g) AG = -397kJ
CO
2
(g) C
graphite
(s) + O
2
(g) AG = 394kJ
C
diamond
(s) C
graphite
(s) AG = -3kJ
This reaction is spontaneous but VERY slow
at 25C and 1atm
Recall: AH

calculations also make use of Hess Law


at 25 C and 1atm.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Recall: AH calculations also make use of Hess Law.
Why is AG so useful?
1.Its relationship to equilibrium
2 It l ti hi t k 2.Its relationship to work.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Gibbs Free Energy and Chemical
8.5, 318
gy
Equilibrium
The real power of AG lies in its relationship to equilibrium.
We can predict in which direction a system under standard
conditions will approach equilibrium (AG = 0). pp q ( )
if AG < 0, process is spontaneous (products favoured)
if AG > 0, reverse process is spontaneous (reactants) p p ( )
if AG = 0, system is at equilibrium
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The Gibbs Free Energy and Chemical
Equilibrium
AG < 0
In terms of energy: at
equilibrium AG = 0 and
h l h the system no longer has
the capacity to do work.
products reactants
AG = 0
AG

= - RT l nK
Thi s i s t he 3
rd
equat i on
t o remember! ! !
where K is the equilibrium constant
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
(This concept will be covered in more depth in module 2)
2. The Gibbs Free Energy and Work.
8.5, 316
2. The Gibbs Free Energy and Work.
A reversible process is done in a specific way so that A reversible process is done in a specific way so that
when undone there is no observable change in the
system or surroundings.
A B
reversible
Remember the First Law?
AU = q + w
h f bl ld b bl For the perfect reversible process we would be able to
extract the maximum work from the internal energy
w is maximized and q is minimized What does q
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
w is maximized and q is minimized. What does q
relate to?
This is the entropy. py
q
r
S
q
r
T
S =
AU
q
r
w
r,max
For a perfectly reversible process, q
r
, thus the gain in
entropy, is minimized.
How do we determine w ??
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
How do we determine w
r, max
??
The Gibbs Free Energy is w
r max
AU
The Gibbs Free Energy is w
r,max
q
r
w
r,max
AG = AH - T AS
AG = w
r, max
The thermodynamic limit to efficiency.
But: perfectly reversible processes are unattainable, p y p ,
yet we can determine AG for any reaction using
thermodynamic tables??
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
AG, AH and AS are St at e Funct ions.
AG = w
r max
When AG is negative, the magnitude of AG is equal to
the maximum useful work obtainable
r, max
the maximum useful work obtainable.
When AG is positive, the magnitude of AG is equal to When AG is positive, the magnitude of AG is equal to
the minimum work that must be expended to make the
process spontaneous.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Why the Gibbs Free Energy ? Why the Gibbs Free Energy ?
Why Free ?? energy that is free to do useful Why Free ?? energy that is free to do useful
work, not pV work done on/by the system, but
electrical, mechanical etc work.
On thi b i o ll l o ee ent op defined On this basis youll also see entropy defined as
the energy that cant do useful work or low
grade energy grade energy.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The other extreme total irreversibility
8.3, 287
The other extreme total irreversibility
AU
q
For a perfectly irreversible process, q is maximized
and work is minimized.
e.g. irreversible battery discharge.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The reality somewhere in between
8.5, 317
The reality somewhere in between
AU
q
r
w
In a real process there will always be losses of heat to
the surroundings the surroundings.
Extra losses will occur due to friction etc.
As l ong as a body r et ai ns t he abi l i t y t o t r ansf er heat t o anot her body
t hat i s at any t emper at ur e above absol ut e zer o Br ow ni an mot i on i s not t hat i s, at any t emper at ur e above absol ut e zer o Br ow ni an mot i on i s not
onl y possi bl e but al so i nevi t abl e. Ei nst ei n, 1905.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Another statement of the second law:
I n any real cyclic process, work is changed t o I n any real cyclic process, work is changed t o
heat in t he surroundings, and t he ent ropy of t he
universe increases.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Example: What is the maximum work obtainable from
2CH
3
OH(l) + 3O
2
(g) 2CO
2
(g) + 4H
2
O(l)
the combustion of methanol
2CH
3
OH(l) 3O
2
(g) 2CO
2
(g) 4H
2
O(l)
AG
f
-166.4 kJ/mol 0 kJ/mol -394.4 kJ/mol -237.2 kJ/mol
AG = (2 x -394.4 + 4 x -237.2) (2 x -166.3) kJ
= -1404.8 kJ
AH
o
= (2 x -393.5 + 4 x -285.8) (2 x -238.7) kJ
1452 8 kJ = -1452.8 kJ
We can expect no better than 96.7 % conversion of the
energy the reaction can provide.
i.e. even done reversibly we still lose 3.3% as heat to the
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
y
surroundings entropy has increased.
Example:
How much work can be gained from a reaction
with the following parameters? g p
AH = +10 kJ; AS = +184 J K
-1
; T = 50K
AG = AH TAS
= 10 000 184 50
800 J = 800 J
Reaction is not spontaneous We must do 800 J of work Reaction is not spontaneous. We must do 800 J of work
in order for reaction to be at equilibrium (e.g. raise the
temp).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p)
Example: The combustion of glucose provides energy for
d l ti it Wh t i th i k nervous and muscular activity. What is the maximum work
available from combustion of 1 mole of glucose at 37
o
C (310K)
and 1atm? AS
o
= 182 4 JK
-1
and 1atm? AS 182.4 JK .
C
6
H
12
O
6(s)
+ 6O
2(g)
6CO
2(g)
+ 6H
2
O
(l)
Know: w
max
= AG, and AG = AH-TAS
So: AH
rxn
= [6xAH(H
2
O
(l)
) + 6xAH(CO
2(g)
)] [6xAH(O
2(g)
) + AH(C
6
H
12
O
6
)]
= -2802.04 kJ/mol
AG
0
= AH
0
- TAS
0
= -2802.04 x10
3
J - (310 K x 182.4 J/K)
= 2858 6 kJ = -2858.6 kJ
Thus: W
max
= 2858.6 kJ/mol glucose burnt.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
MW glucose = 180g/mol, then 2858.6/180 = 15.9 kJ/gram glucose.
In order to climb 3 0 m vertically a 70 kg person would In order to climb 3.0 m vertically, a 70 kg person would
need: (70 x 9.8) x 3 = 2.06kJ of energy.
We have 15.9 kJ/gram of glucose, so 70kg person would
need to burn: 2.06/15.9 = 0.13 grams glucose.
In reality, much more than this would be required due to
heat losses (ever tried climbing 3 m vertically!!) heat losses (ever tried climbing 3 m vertically!!).
Other examples: See Page 317, Blackman.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The problem of rust?
4Fe(s) + 3O
2
(g) 2Fe
2
O
3
(s) AS
univ
= 4980J/K
The problem of rust?
4 mol Fe So: AG for rusting (at 298 K)
+
4 mol Fe So: AG for rusting (at 298 K)
AG = -TAS
univ
= AH TAS
3 mol O
2
= -298 K 4980 J/K
= - 1484.0 kJ
2 mol Fe
2
O
3
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What you should be able to do at this y
stage:
1. Explain how the Gibbs Free Energy relates to system variables.
2 D t i t it i th Gibb F E ti 2. Determine spontaneity using the Gibbs Free Energy equation.
3. Predict how temperature will affect AG for a reaction.
4. Correlate the Gibbs Free Energy with the work obtainable from
a reaction.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Entropy and the real world Entropy and the real world
1. Aircraft Air Quality : www.boeing.com 1. Aircraft Air Quality : www.boeing.com
2. Energy Microgeneration : Catalyst (ABC).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Entropy and the real world - www.boeing .com - air
The cabin air system in today's jetliners is designed to provide a safe, comfortable
bi i t t i i ltit d th t h d f 40 000 f t
quality.
cabin environment at cruising altitudes that can reach upwards of 40,000 feet.
At those altitudes, the cabin must be pressurized to enable passengers and crew to
breathe normally By government regulation the cabin pressure cannot be less at breathe normally. By government regulation, the cabin pressure cannot be less, at
maximum cruise altitude, than the equivalent of outside air pressure at 8,000 feet.
In addition to pressurization, the cabin air system controls air flow, air filtration and
temperature temperature .
Can you see what a major problem is with this? Can you see what a major problem is with this?
HEAT: the air must be compressed (uses energy)
hi h l lt i h ti Thi i th l d f which also results in heating. This is then cooled for
the cabin.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Entropy and the real world - www.boeing .com - air
E it f i d i t t d f th i h th ff t f
quality.
Every unit of pressurized air extracted from the engine core has the effect of
reducing fan thrust by an even greater amount, and that degrades fuel efficiency
more severely on this type of engine than on the older type. By providing the cabin
with a mixture of about 50 percent outside air taken from the compressor and 50 with a mixture of about 50 percent outside air taken from the compressor and 50
percent recirculated air, a balance has been achieved that maintains a high level
of cabin air quality, good fuel efficiency and less impact to our environment.
Airlines can save money by reducing the number of times
new air is brought into the cabin and thus reducing energy
losses due to compression/refrigeration!!
i E t h j i t i ll i.e. Entropy has a major impact on economics all
due to the fact that gas compression is not a
t !!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
spontaneous process!!
Catalyst - ABC.net .au Catalyst ABC.net .au
UK Microgen
Joni ca: That must terrify the energy companies. Al l an: It certainly does terrify the energy dinosaurs.
Narrat i on: So how did he do it? Well, when Allan was asked to update the towns heating systems, instead, he installed these.
Al l J : Thi i th W ki g t t bi d h t d t ti Al l an Jones: This is the Woking town centre combined heat and power station.
Joni ca: Thats not a power station, its too small. Al l an: Well that gener at es el ect r i ci t y, and i t r ecover s t he heat f r om t hat el ect r i ci t y and t hen
pi pes t hat under gr ound t o suppl y heat i ng, hot wat er .
Narrat i on: Lets be clear this is the combined heat power station the rest is carpark. p p
Combined heat and power is not new Manhattan was set up with it in the 1880s.
But when modern, centralised power stations were invented, CHP was quietly abandoned Manhattans surrounds are on the grid.
In ener gy t er ms t hough cent r al i sed power st at i ons ar e f ar l ess ef f i ci ent In ener gy t er ms, t hough, cent r al i sed power st at i ons ar e f ar l ess ef f i ci ent .
2/ 3 of t he ener gy pr oduced i s t hr own away i nt o t he at mospher e as heat wi t h f ur t her l osses over t he gr i d.
Al l an Jones: From their point of view they just generate electricity, throw the heat away, and the gas companies provide gas for peoples boilers so
its a double whammy. Not only are they throwing energy away t hey r e usi ng anot her l ot of ener gy t o do somet hi ng t hat coul d have been done
f h h I j l f d h i f li h f r om t he wast e heat . Its just a complete waste of energy and the primary cause of climate change.
Narrat i on: Annoyed by what he calls the rubbish way things are done, Allan installed 80 combined heat power units in the town, complemented by
rows and rows of solar panels.
By 2004, humble Woking was producing 80% of its own energy. And in just 10 years it had dropped its CO
2
emissions by a mind-boggling 77%
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
y , g p g gy j y pp
2
y gg g
atmosphere
q w
Conventional centralised power station
(Tarong Power Station q q
waste
w (Tarong Power Station,
180 kilometres west of Brisbane)
q
r
Electricity grid
atmosphere
Decentralised power station: The future ??
One block of houses one CHP unit
w q
r
q
useful?
Hot water system
General heating
Electricity
Entropy may be low grade energy but
can 21st century thermodynamics make
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
g
What else???
y y
it do any work at all ??
These are t he most i mport ant key concept s f rom t hi s modul e: Summary!
1. The t hree l aws of t hermodynami cs:
1. Energy is always conserved, it cannot be destroyed only transferred from one place to another.
2. In spontaneous processes the entropy of the universe does increase. (Nature proceeds towards
more probable states)
3. The entropy of a perfectly ordered crystal ay 0 K is 0.
2. St at e f unct i ons:
1. Value only depends only on state of system, not how it got there! Circular integral =0
2. Can use law of Hess to calculate values of thermodynamic quantities from each other
3. Inner ener gy: AU= q + w = q
v
(potential energy of a system)
4. Ent hal py: AH = AU +pAV = q
p
(Heat transferred at constant pressure => exo/endothermic)
5. Ent r opy:
1. Statistical Definition: S = measure for the distribution of energy within a state (+ whence
the probability of a state) the probability of a state).
2. Thermodynamic definition: S = q
r
/T (from Carnot cycle)
6. Gi bbs f r ee ent hal py: AG = AH - TAS. AG = -TAS
univ
3 Th t h t i t t t i 3. The t hree most i mport ant equat i ons:
1. Ideal Gas equation: pV = nRT
2. Gibbs equation: AG= AH TAS
3 Gibbs enthalpy and K: AG= RT l nK
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
3. Gibbs enthalpy and K: AG= RT l nK
CHEM1020 CHEM1020
Module 1: Lecture 10
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Affected by:
temperature,
Links to
Equilibrium
p ,
pressure,
concentrations
Thermodynamics
Homogeneous
Module 1
Heterogeneous
Module 2
Chemical
Reactions
Acid/Base:
Module 4
Phase
Changes
Solubility
Electro-
chemistry:
Module 2
U d i i CHEM2002 CHEM2056 BIOC2000
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Underpinning CHEM2002, CHEM2056, BIOC2000
Note: In the next few lectures we use specific examples to teach key ideas
(concepts) you are expected to be able to apply these ideas to any
equilibrium reaction. q
Examples of equilibrium processes in real life tend to be complex systems so
we will begin with simple examples. we will begin with simple examples.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
http://www.rsc.org/education/teachers/learnnet/cfb/transport.htm
Explore your existing understanding of equilibrium
Write the balanced equation for the decomposition of dinitrogen tetroxide
to nitrogen dioxide: to nitrogen dioxide:
) ( O N
4 2
g ) ( 2NO
2
g ) ( O N
4 2
g ) ( 2NO
2
g
Write the balanced equation for the dimerisation reaction of nitrogen
di id t f di it t t id dioxide to form dinitrogen tetroxide:
) ( O N ) ( 2NO ) ( O N
4 2
g ) ( 2NO
2
g
Write the balanced equilibrium expression for the reaction above: Write the balanced equilibrium expression for the reaction above:
) ( O N g
) ( 2NO
) ( O N g ) ( 2NO g
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
) ( O N
4 2
g
) ( 2NO
2
g
) ( O N
4 2
g ) ( 2NO
2
g
Bl ackman Chapt er 9
Consider . . .
dinitrogen
tetroxide
nitrogen
dioxide
N
2
O
4
(g) is in a sealed tube closed system - begins to dissociate
t f NO ( ) hi h i t i lt l b i t bi t to form NO
2
(g), which in turn simultaneously begins to recombine to
form N
2
O
4
(g)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Equilibrium is a dynamic process (it can respond to change!)
p 334
We can observe the progress of a reaction by monitoring concentration as
a function of time.
The initial concentration of N
2
O
4
decreases with time
Simultaneously the concentration of NO
2
increases with time
Equilibrium is reached when there is no NET change
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Equilibrium is reached when there is no NET change
) ( O N
4 2
g ) ( 2NO
2
g ) (
4 2
g
2
Note: starting with same number of atoms Note: starting with same number of atoms
The same equilibrium will be reached by starting with either N
2
O
4
(g) or
ith NO ( ) with NO
2
(g)
This is an example of a Homogeneous equilibrium
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The position of chemical equilibrium can be expressed in terms of
the equi l i bri um const ant :
) ( O N
4 2
g ) ( 2NO
2
g
After concentrations have stopped changing, find that:
| |
| |
C 25 at 10 61 . 4
NO
o 3
2
2
= = K
regardless of starting concentrations This ratio is known as the
| |
C 25 at 10 61 . 4
O N
4 2

c
K
regardless of starting concentrations. This ratio is known as the
equilibrium expression for the reaction and results in the
equi l i br i um const ant , K
c
.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Generic representation of the expression for the p p
Equilibrium constant:
p 335
Note:
1. [A] refers to the equilibrium concentration of A in mol L
-1
(or
M).
2. K
c
is dimensionless in the sub-discipline of physical chemistry.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
The val ue of K
c
i s dependent on t emperat ure
) ( O N
4 2
g ) ( 2NO
2
g
C 100 at 212 0
] NO [
2
2
= = K C 100 at 212 . 0
] O N [
4 2
c
K
2
C 25 at 10 61 . 4
] O N [
] NO [
3
4 2
2
2
= =

c
K
K
c
... What does the magnitude tell us?
At equilibrium, concentrations of reactants and products will be of the
same order of magnitude at 100
o
C.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/lechv17.swf
K
c
... What does the magnitude tell us? K
c
... What does the magnitude tell us?
Compare:
2H
2
(g) + O
2
(g) 2H
2
O(g)
] O H [
2
298K at 10 1 . 9
] [O ] H [
] O H [
80
2
2
2
2
2
= =
c
K
N (g) + O (g) 2NO(g) N
2
(g) + O
2
(g) 2NO(g)
298K at 10 8 . 4
] NO [
31
2

= =
c
K
] [O ] N [
2 2
c
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
So the magnitude of K gives us an indication of the position of the So the magnitude of K gives us an indication of the position of the
equilibrium
K >> 1 : products favoured
K 1 t t f d K << 1 : reactants favoured
K = 1 : equilibrium concentrations K = 1 : equilibrium concentrations
will be comparable
When is an equilibrium positioned in the middle?
Rule of thumb
When K
c
is in the range of 0.01-100 (10
-2
10
2
)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
c
g ( )
The equilibrium constant for the following reaction is
K = 4 x 10
5
at 400K K
c
4 x 10 at 400K
CO(g) + Cl
2
(g) COCl
2
(g)
What is the position of this equilibrium
at this temperature?
1. Far to the left
2 Far to the right 2. Far to the right
3. Close to the middle
(equivalent concentrations (equivalent concentrations
of reactants and products)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
An equi l i br i um expr essi on can be wr i t t en i n mor e t han
Wh t h t l f K f one way What happens t o val ue of K
c
f or a r ever se
r eact i on?
If the opposite reaction is considered (i.e the equation is written in
reverse) then K
c
is inverted.
e.g. ) ( O N
4 2
g ) ( 2NO
2
g
] NO [
2
C 25 at 10 61 . 4
] O N [
] NO [
3
4 2
2
2
= =

c
K
inverted
) ( 2NO
2
g ) ( O N
4 2
g
2
) (
4 2
g
C 25 at 217
] NO [
] O N [
2
4 2
= =
c
K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
] NO [
2
2
Usi ng t he Equi l i bri um Const ant t o predi ct composi t i on g q p p
The equilibrium constant is useful because it enables us to calculate
equilibrium concentrations of reactants and products: equilibrium concentrations of reactants and products:
) ( O N
4 2
g ) ( 2NO
2
g
The equilibrium expression is:
] NO [
3
2
2
C 25 at 10 x 4.61
] O N [
] NO [
3 -
4 2
2
= =
c
K
If, at equilibrium
| | M 01 . 0 NO
2
= , then
| |
| |
M 0.0217
NO
O N
2
2
4 2
= =
K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
c
K
Usi ng t he Equi l i bri um Const ant t o predi ct composi t i on g q p p
The equilibrium constant also enables us to calculate equilibrium
concentrations of reactants and products from any initial concentrations of reactants and products from any initial
concentrations, more complex:
] NO [
2
C 25 at 10 x 4.61
] O N [
] NO [
3 -
4 2
2
2
= =
c
K
) ( O N
4 2
g ) ( 2NO
2
g
If the initial concentration of N
2
O
4
is 0.50 M, what are the equilibrium
concentrations of each gas involved? concentrations of each gas involved?
To solve this type of problem we can use an ICE Table where we To solve this type of problem we can use an ICE Table where we
represent the concentrations of reactant and product species as a
variable and use algebra!!
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
St rat egy: St rat egy:
The concentration of the reactant will have decreased by the an amount
(x) at equilibrium and the concentration of the product will have (x) at equilibrium, and the concentration of the product will have
increased to be (2x).
) ( O N ) ( 2NO
Initial conc: 0.50 0.00
) ( O N
4 2
g ) ( 2NO
2
g
Change: -x +2x
Equilibrium conc: (0.50 x) 2x
Use the stoichiometry of the equation to determine the relative amounts
at equilibrium
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
q
The equilibrium constant is given by:
] NO [
2
C 25 at 10 x 4.61
] O N [
] NO [
3 -
4 2
2
2
= =
c
K
( ) 2
2
( )
( ) x
x

=

50 . 0
2
10 61 . 4
2
3
substituting
Which becomes a quadratic equation and when solved for x:
0 023 x = 0.023
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Homework: Write out the steps to solve this equation.
S th ilib i t ti So the equilibrium concentrations are:
[N
2
O
4
] = (0.50 0.023) M = 0.477 M [N
2
O
4
] (0.50 0.023) M 0.477 M
[NO
2
] = 2 x 0.023 M = 0.046 M
0 48 M 0 05 M
) ( O N
4 2
g ) ( 2NO
2
g
0.48 M 0.05 M
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Appl yi ng underst andi ng of equi l i bri um:
The amount of nitrogen fixed naturally by plants
Appl yi ng underst andi ng of equi l i bri um:
is too low to meet our demands for food supply -
so the Haber process is one of the most important
commercial processes. co e c al p ocesses.
Liquid ammonia produced by the Haber process is either added directly to
soil as a fertiliser or is converted into ammonium salts (phosphates &
nitrates) for the same purpose nitrates) for the same purpose.
k l h
) ( H ) ( N
2 2
g g +
) ( NH
3
g
Homework: Balance this equation:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
) ( ) (
2 2
g g
3
Homework:
At 127 C the following equilibrium concentrations were found:
Homework:
[H
2
] = 3.1x10
-3
M
[N ] = 8 5x10
-1
M [N
2
] = 8.5x10
1
M
[NH
3
] = 3.1x10
-2
M
Write the equilibrium expression for this reaction
Calculate the value of K at 127 C for this reaction Calculate the value of K
c
at 127 C for this reaction.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
CHEM1020 CHEM1020
Module 1: Lecture 11
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Where we left off
) ( H 3 ) ( N
2 2
g g + ) ( NH 2
3
g
) ( H ) ( N
3 1
) ( NH
or
) ( H ) ( N
2 2
3
2 2
1
g g + ) ( NH
3
g
At 127 C the following equilibrium concentrations were
found:
[H ] 3 1 10
3
M [H
2
] = 3.1x10
-3
M
[N
2
] = 8.5x10
-1
M
[NH ] 3 1 10
2
M [NH
3
] = 3.1x10
-2
M
Write the equilibrium expression for this reaction
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Calculate the value of K
c
at 127 C for this reaction.
Writing and substituting into the equilibrium expression
there is more than one correct answer!
) ( H 3 ) ( N g g + ) ( NH 2 g
| | ( )
4
2
2
2
10 1 3 NH

) ( H 3 ) ( N
2 2
g g + ) ( NH 2
3
g
| |
| || |
( )
( )( )
4
3
3 1
3
2 2
3
10 8 . 3
10 1 . 3 10 5 . 8
10 1 . 3
H N
NH
=


= =

c
K
What is the value of K* for the reverse reaction?
) ( H 3 ) ( N
2 2
g g + ) ( NH 2
3
g
| || |
| |
5
4 2
3
2 2 *
10 6 . 2
1 1 H N

= = = = K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
| |
4 2
3
10 6 . 2
10 8 . 3 NH
c
K
K
How will the equilibrium constant change if we alter the q g
coefficients that we use to balance the equation for the
Haber process?
) ( H ) ( N
2 2
3
2 2
1
g g + ) ( NH
3
g
1
| |
K
c
When would we use
this stoichiometry?
| |
| | | |
| |
| || |
2
3
2 2
2
3 3
2
3
2
1
|
|
.
|

\
|
= = ' '
H N
NH
H N
NH
K
| | | |
| || |
( )
2 4
2 2
2 2
10 9 . 1 10 8 . 3
2
1
2
1
= = = ' '
. \
c
K K
H N
H N
( )
c
b b
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Note that (x
a
)
b
= x
ab
For the following reaction, K
c
= 7.9 x 10
11
at 500 K
H ( ) B ( ) 2HB ( ) H
(2)
(g) + Br
2
(g) 2HBr(g)
Calculate K for the reaction: Calculate K
c
for the reaction:
4HBr 2H
2
+ 2Br
2
1 1/7 9 x 10
11
1. 1/7.9 x 10
11
2. (7.9 x 10
11
)
2
3. 1/[(7.9 x 10
11
)
2
]
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Gas Phase Equi l i bri um (Homogeneous)
So far we have used the equilibrium constant in terms of So far we have used the equilibrium constant in terms of
concentration when we consider gases we can also express K
in terms of the part i al pressures of the gases. in terms of the part i al pressures of the gases.
) ( O N
4 2
g ) ( 2NO
2
g
) (
2
2
NO
P
K =
Us all se standard state of 1 atm so press res e pressed in
) (
4 2
O N
p
P
K =
Usually use standard state of 1 atm, so pressures expressed in
units of atmospheres, and equilibrium constants quoted with no
dimensions. dimensions.
Alternatively: pressure in Pa divided by standard pressure of
1x10
5
Pa (1 atm) refer Chemistry p 337
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
1x10
5
Pa (1 atm) refer Chemistry p 337.
How are K
c
and K
P
rel at ed? How are K
c
and K
P
rel at ed?
Remember that pressure is related to concentration
th h th id l ti
Since concentration is
P n
through the ideal gas equation.
RT V
=
| | K
K
P
RT
P
|
.
|

\
|
2
NO
2
2
2
NO
n
RT K K
A
= ) (
or
| |
| | RT
K
P
RT
P
c
=
|
.
|

\
|
. \
= =
4 O
2
N
4 2
2
O N
c P
RT K K = ) (
or
. \
where An is change in moles of gas as reactants are
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
g g
converted to products
Example: Example:
) ( O N
4 2
g ) ( 2NO
2
g
C 25 at 10 x 4.61
] O N [
] NO [
3 -
4 2
2
2
= =
c
K
] [
4 2
What is the value of K
p
?
p
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p337 (9.3)
n
c P
RT K K
A
= ) (
K
c
= 4.61 x 10
-3
R = 0.08206 atm L mol
-1
K
-1
R 0.08206 atm L mol K
T = 298 K (273 + 25
o
C)
An = +1 An 1
| |
1 1 3
10 13 . 1 298 08206 . 0 10 61 . 4
+
= =
P
K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Practice Question
One possible way of removing NO
from the exhaust of a petrol engine is
Practice Question
from the exhaust of a petrol engine is
to react it with CO in the presence of
suitable catalyst.
2NO(g) + 2CO(g) N (g) + 2CO (g) 2NO(g) + 2CO(g) N
2
(g) + 2CO
2
(g)
At 300
o
C this reaction has K
c
= 2.2 x 10
59
.
What is K at 300
o
C? What is K
p
at 300
o
C?
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Always check units!
Caution!!
It is very important that correct units are used in this
Always check units!
Caution!!
equation. This relates to units of the gas constant, R.
Since K or K must be in mol L
-1
& the equilibrium pressure Since K
c
or K
p
must be in mol L
1
& the equilibrium pressure
be in atm, respectively, we must use R = 0.08206 atm L mol
-1
K
-1
K
Otherwise a conversion must be used.
Note:
Blackman Chemistry uses different units which makes these calculations Blackman Chemistry uses different units which makes these calculations
very complex due to unit conversions. Refer to p 338-9.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Now t hat you can wri t e t he expressi on f or an equi l i bri um . .
Y h t b bl t di t h t ill h h h You have to be able to predict what will happen when a change
occurs to the system:
Change in concentration
Change in pressure g p
Change in volume
Change in temperature
There are two strategies for doing this:
Le Chateliers principle (qualitative).
Reaction quotient Q (quantitative) Reaction quotient, Q (quantitative).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Predi ct i ng Equi l i bri um Response t o Change
What factors will influence the position of the
Predi ct i ng Equi l i bri um Response t o Change
equilibrium:
A usef ul pri nci pl e was devel oped by
L Ch t l i i 1884 i l Le Chat el i er i n 1884, si mpl y .
If a chemical equilibrium is disturbed If a chemical equilibrium is disturbed
by a change in the conditions of the
system, it will respond by moving system, it will respond by moving
towards a new equilibrium state in
the direction which reduces the
effect of the change.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p 352
Ef f ect of Change i n Concent r at i on on Equi l i br i um:
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/lechv17.swf
) ( FeSCN
2
aq
+
) ( SCN ) ( Fe
3
aq aq
+
+
Appl yi ng Le Chat el i er s pri nci pl e
Addition of NaSCN leads to increase of [SCN
-
]. Observe
that [FeSCN
2+
] increases and [Fe
3+
] decreases to offset the
pp y g p p
that [FeSCN
2+
] increases and [Fe
3+
] decreases to offset the
change.
Additi f l t i C O
2
hi h bi d F
3+
i l d Addition of oxalate ions, C
2
O
4
2-
, which bind Fe
3+
ions, leads
to a decrease in the concentration of FeSCN
2+
and increase
in [SCN
-
]
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
in [SCN ].
When a change is made in the concentration of reactants or
d t th t i l g t ilib i b t till products, the system is no longer at equilibrium but we still
use this expression:
d c
Q
] D [ ] C [
Q represents the mass balance
when the system is no longer
b
Q
] B [ [A]
] [ ] [
a
=
when the system is no longer
at equilibrium.
[A] refers to the concentration of A in mol L
-1
(or M).
Then we compare the reaction quotient Q with K Then we compare the reaction quotient, Q with K
c
If Q < K
c
the reaction will move in the forward direction If Q K
c
the reaction will move in the forward direction
If Q > K
c
the reaction will move in the reverse direction
Important!
At equilibrium Q = K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
At equilibrium, Q = K
c
Usi ng Q t o predi ct t he response of equi l i bri um t o g Q p p q
change i n concent rat i on:
Qualitatively: If we
add more NO
2
how add more NO
2
, how
will the system
respond?
) ( O N
4 2
g ) ( 2NO
2
g
It will move to restore equilibrium . . .
We can use the reaction quotient, Q, to predict in which
direction it will move
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
What will happen when we increase [NO
2
] - discuss? What will happen when we increase [NO
2
] discuss?
| |
2
2
] NO [
= Q
| |
4 2
O N
Q
By adding more NO
2
gas we will increase the concentration
of a product of a product.
So Q > K
c
and the reaction will proceed in the reverse
direction to return to equilibrium! direction to return to equilibrium!
This means that more reactants form and we end up with
more NO
2
and more N
2
O
4
than before the addition.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
more NO
2
and more N
2
O
4
than before the addition.
Comparing Q and K Comparing Q and K
c
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Homework Homework
2SO
3
(g) 2SO
2
(g) + O
2
(g)
3
(g)
2
(g)
2
(g)
At 1000 K the value of K = 4 08 x 10
-3
At 1000 K, the value of K
c
= 4.08 x 10
W i h i f K ! Write the expression for K
c
!
If we mix together the following reactants:
[SO
3
] = 2 x 10
-3
M
[SO ] = 5 x 10
-3
M [SO
2
] = 5 x 10
-3
M
[O
2
] = 3 x 10
-2
M
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
In which direction will the reaction proceed towards equilibrium?
CHEM1020 CHEM1020
Module 1: Lecture 12
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Ef f ect of Change i n Pr essur e (or Vol ume) on Equi l i br i um f f f g ( ) q
Very important if gases are involved . . . pressure can be
h d i th t changed in three separate ways:
1. Add or remove a gaseous reactant or product
2. Add an inert gas (eg helium)
3. Change the volume
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
p 352
1. Add or remove a gaseous reactant or product g p
Changes the concentration, since concentration = n/V, so
t t b f treat as before.
2 Add an inert gas (eg helium) 2. Add an inert gas (eg helium)
No change in concentrations, so equilibrium position g , q p
unaffected.
3 Ch th l
Concentration of gaseous species changes, but may or
3. Change the volume
g p g , y
may not change equilibrium. This depends on the
stoichiometry of the reaction.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Experi ment al Observat i on:
What is the effect of decreasing the volume of this system
at equilibrium at constant temperature?
p
q p
) ( O N
4 2
g ) ( 2NO
2
g
Observe: The concentration of both species increases.
System responds to change by shifting balance to the side System responds to change by shifting balance to the side
with fewer moles of gases, ie left.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Vol & equil
Le Chatelier!
Thi nki ng i n t erms of r eact i on quot i ent , Q: Thi nki ng i n t erms of r eact i on quot i ent , Q:
| |
| |
2
2
O N
NO
= Q (any conditions)
Initially, Q = K, but after the decrease in volume, Q > K.
| |
4 2
O N
Initially, Q K, but after the decrease in volume, Q > K.
System adjusts by decreasing [NO
2
] and increasing [N
2
O
4
]
until Q = K once more.
The value of K remains constant.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Effect of decreasing volume(by increasing pressure) g ( y g p )
Volume change:
l t
Initial
equilibrium
no longer at
equilibrium
Final
equilibrium
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Compare the number of molecules at equilibrium in (a) and (c)
) ( H 3 ) ( N
2 2
g g + ) ( NH 2
3
g ) ( ) (
2 2
g g ) (
3
g
11 molecules in (a) 9 molecules in (c) 11 molecules in (a) 9 molecules in (c)
System has responded to the reduction in volume by
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
System has responded to the reduction in volume by
reducing the number of molecules.
Homework: Homework:
Predict what would happen if you reduced the volume of a Predict what would happen if you reduced the volume of a
vessel in which the following equilibrium existed:
2HI(g) H
2
(g) + I
2
(g)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Ef f ect of Temper at ur e on Equi l i br i um f f f p q
If temperature is changed, the val ue of K
h Di ti f h d d changes. Direction of change depends on
the sign of AH
O 6 C Cl
2
( )

+
Cl 4 O H C
2
O H 6 CoCl
2
2
4
+

( )
+
+ Cl 4 O H Co
2
6 2
blue pink
Forward reaction is exothermic (H < 0).
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Cobalt temp final
What will be the effect of applying heat to this system? What will be the effect of applying heat to this system?
O H 6 CoCl
2
2
4
+

( )
+
+ Cl 4 O H Co
2
6 2
+ kJ
blue pink
Heating forces equilibrium to left, cooling to right, ie
heating favours an endothermic reaction heating favours an endothermic reaction
C
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Le Chatelier!
Consider this equilibrium: Consider this equilibrium:
N
2
O
4
(g) 2NO
2
(g) AH
o
= + 56 9 kJ N
2
O
4
(g) 2NO
2
(g) AH 56.9 kJ
What effect would raising the temperature have?
1. No effect
2. An increase in the amount of NO
2
(g)
3 An increase in the amount of N
2
O
4
(g) 3. An increase in the amount of N
2
O
4
(g)
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
N
2
O
4
effect of T
An increase in the number of NO
2
molecules. The
reaction is endothermic and so the input of heat
energy as a reactant shifts the equilibrium to the
right.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
How do we explain effect of temperature quantitatively? How do we explain effect of temperature quantitatively?
The 1
st
winner of the Nobel
Prize in Chemistry Prize in Chemistry
Jacobus Henricus vant Hoff Jacobus Henricus van t Hoff
For his work in thermodynamics
But
Al d i d h b Also determined that carbon
forms tetrahedral rather than
square planar structures
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
square planar structures.
Vant Hoff Equation
ln H K d A
Van t Hoff Equation
p 355
2
ln
RT
H
dT
K d A
=
AH is positive AH is negative
Exothermic
Increasing T decreases K so
Endothermic
Increasing T increases K so
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Increasing T decreases K so
reactants are favoured
Increasing T increases K so
products are favoured
2
ln
RT
H
dT
K d A
=
| | A | |
0
1 1 H K
RT dT
Integrate
|
|
.
|

\
|

A
=
|
|
.
|

\
|
2 1
0
2
1
1 1
ln
T T R
H
K
K
When we know the standard enthalpy and K at one
temperature, we are able to calculate the K at a different
temperature temperature.
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Temperat ure Dependence of K
We can deduce the temperature dependence of the
ilib i i h f ll i equilibrium constant using the following:
0 0 0
ln S T H K RT G A A = = A ln S T H K RT G A A = = A
S H
K
0 0
ln
A
+
A
=
S H
R RT
K
0 0
1
ln
A
|
|

|
A
+ =
R T R
+
|
.
|

\
|
=
This is in the form of linear equation y = mx + c with This is in the form of linear equation y = mx + c, with
slope = -AH / R and y-intercept AS / R
Assumes temperature independence of H and S
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Assumes temperature independence of H and S.
p 350
S H A
|
|

| A
0 0
1
R
S
T R
H
K
A
+
|
.
|

\
| A
=
1
ln
c x m y + =
l
n

K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
1/T
The two equations are related: The two equations are related:
If at temp. T
1
we have K
1
and at temp. T
2
, K
2
, then
R
S
T R
H
K
0
1
0
1
1
ln
A
+
|
|
.
|

\
| A
=
S H
K
R T R
0 0
2
1
1
ln
A
+
|
|
|

| A
=
. \
R T R
K
2
2
ln +
|
|
.

\
=
S bt t SECOND ti f FIRST Subtract SECOND equation from FIRST:
| |
A
| |
0
1 1 H K
|
|
.
|

\
|

A
=
|
.
|

\
|
2 1
1
1 1
2
ln
T T R
H
K
K
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
. \
. \
2 1
Subtract SECOND equation from FIRST:
A
+
|
|
.
|

\
| A
=
R
S
T R
H
K
0
1
0
1
1
ln
q
(

A
+
|
|
.
|

\
| A
=
. \
R
S
T R
H
K
R T R
0 0
2
1
1
ln

|
.

\
R T R
2
( )
(
(

|
|
|

| A
|
|
|

| A
0 0
1 1
) ln( ln
H H
K K ( )
(

|
|
.

\

|
|
.

\
=
2 1
2 1
) ln( ln
T R T R
K K
|
|
|

A
=
|
|
|

|
0
1
1 1
ln
H K
So:
|
|
.

\
=
|
|
.

\ 2 1 2
ln
T T R K
So:
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Problem:
N (g) + 3H (g) 2NH (g)
Problem:
This reaction is exothermic
N
2
(g) + 3H
2
(g) 2NH
3
(g)
This reaction is exothermic
By using the equation below, explain the observed values
for K at various temperatures for K at various temperatures
S H
0 0
A A
R
S
RT
H
K
0 0
ln
A
+
A
=
R
S
T R
H
0 0
1 A
+
|
.
|

\
|
A
=
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Temperature dependence of K Temperature dependence of K
N
2
(g) + 3H
2
(g) 2NH
3
(g) - 92.38 kJ
Exothermic process: AH
0
< 0
For an exothermic process the slope is For an exothermic process the slope is
positive and therefore as the temperature
increases the equilibrium constant
decreases
S H
0 0
A A
n

K
S
R
S
RT
H
K
0 0
0 0
ln
A
| |
A
A
+
A
=
l
n
R
S
T R
H
0 0
1 A
+
|
.
|

\
|
A
=
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
Sl ope!
1/T
The applicability of the vant Hoff equation at two
| |
A
| |
0
1 1 H K
The applicability of the van t Hoff equation at two
specified temperatures:
|
|
.
|

\
|

A
=
|
|
.
|

\
|
2 1 2
1
1 1
ln
T T R
H
K
K
T
1
= 500 K
K
1
= 90
T = 800 K
. \ . \ 2 1 2
T
2
= 800 K
K
2
= ?
AH
o
= - 92 kJ
|
|
|

| A
=
0
1 1
ln ln
H
K K
AH 92 kJ
|
|
.

\
=
2 1
2 1
ln ln
T T R
K K
ln(90)- ln K
2
= 92 x 10
3
1 1
8.314 500 800
4.50 lnK
2
= 8.30
ln K
2
= -3.80
School of Chemistry & Molecular Biosciences CHEM1020 Sem 2 / 2011 Module 1: Thermodynamics & Equilibrium
ln K
2
3.80
K
2
= 0.02