Thermodynamics

Dr Onesmus Munyati
Department of Chemistry
University of Zambia, Lusaka, Zambia
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2
Thermodynamics
What is thermodynamics?

concerned with the interconversion of
thermal energy and other forms of
energy
Provides useful guideline to
understanding energy changes in
chemical reactions and processes
Enables us make predictions of the
direction of processes
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Thermodynamics is concerned with
changes in the state of the system as
defined by macroscopic parameters
such as composition, volume, pressure,
temperature and energy
We monitor the changes in these
parameters from one state to another
What happens to n, V, P, T and E
during a physical or chemical
processing?
Can we account for the energy changes
accompanying such processes
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Language of thermodynamics
Thermodynamic system
A thermodynamic system is that
part of the universe that is under
consideration

Experimental set-up in the lab
Biological cell
Wine fermentation tank
etc

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The system is separated from the
rest of the universe by a real or
imaginary boundary that separates
the system from the surroundings
The surroundings are where we are
and the rest of the is the universe
The type of system is often
characterised by the nature of the
boundary: open, closed or isolated
Types of Systems
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System can exchange both heat and matter with
their surroundings (e.g. open beaker, boiling kettle,
open gas cylinder)
Open system
Energy can be transferred between the system and
surroundings but not matter (e.g. closed gas
cylinder etc)

Closed system
Isolated system
Systems are completely isolated from their
surroundings (e.g. insulated container, thermos flask
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State and non-state functions
State of the system is defined by macroscopic
properties e.g. composition, volume, pressure and
energy
In thermodynamics we are concerned with changes
related to these properties
Such functions depend only the initial and final
states of the system does not depend on the path
taken (used)
Elevation
Potential energy
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Non-state function are path dependant
e.g. work and heat depends on the route
used (see the climber!)
In moving from state 1 to state 2 , that is
different amount of work will be done
depending on the path used
The climber will expend different amount
of effort using the two routes
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Learning check!
How much work is done if a 1.5 m
tall woman lifts a pile of firewood
(15 kg in weight) on to her head to
carry home for cooking?
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Work (w)
Common language when we do
something lift, push, dig etc
When an object is moved against an
opposing force - work is done
Chemical reactions do work when
electrons are driven through a metal
wire
In chemical systems commonly
encountered work is volume-
pressure
Volume changes for example occur
due to disappearance or
appearance of new gaseous
products
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Consider a gas
confined in cylinder
with a movable piston
We can place some
weights on the piston
to exert a force F over
the cross-section area
A, producing a
pressure P.
Example work of expansion
Cylinder
Gas
Piston
12
m
2

h
m
1
m
2

V
1

m
1

V
2

Expansion
If we removed one the weights the volume
changes from V
1
to V
2
as the piston
moves through a distance h.
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Pressure is defined as the force per
unit area
A
F
p =
Rearrange to express the force in terms
of pressure and area
A x p F =
From classical mechanics
Work (w) = force (F) x distance (h)
= p x A x h
w = pAV
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Problem to consider?
A hydrocarbon is burned in a container
with a movable piston with a cross-section
area of 0.5 m
2
. If the piston moved a
distance of 30 cm against a pressure of 1
atm, how much work is done in the
expansion?
15
Solution

In expanding, the piston sweeps through a volume =
cross section area x distance covered.
Change in volume V = 0.5 m
2
x 0.3 m = 0.15 m
3
, P
= 1 atm = 101325 Nm
2
w = P
ex
AV
= (101325 Nm
2
x 0.15 m
3
)
= 15 199 J
= 15.2 kJ

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Heat (q)
Heat is the thermal energy that is
transferred when two bodies are in
contact. It flows from a warmer body to a
cooler one.
Energy is transferred between the two
bodies until the average kinetic energy
between them are the same condition
of thermal equilibrium
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Chemical changes and heat
Energy is either evolved or released during
chemical changes
A process in which heat is released to the
surroundings is known as an exothermic
process e.g. combustion of hydrocarbons.

Energy exits system, - E
E
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An endothermic process in one in which energy
is absorbed by the system e.g. vaporization of
water
Heat is absorbed from the surroundings by the
system.
Consequently the temperature of the
surroundings will tend to drop as the reaction or
process proceeds.
Energy added to
system, + E

E
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Surroundings
Exothermic, heat
released to the
surroundings
Endothermic, heat
absorbed from the
surroundings
System
Summary
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Different types of energy
Kinetic energy

Energy associated with motion of matter and is
given by the equation
2
mv
2
1
K.E. =
Examples: molecules in motion, rockets
and missiles, moving motor vehicle etc
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Potential energy

Energy that a body has by
virtual of its position in a
force field.Typical examples
of force fields: gravitational,
electrical and magnetic
fields
Also be associated with
charged particles or species
such as cations and anions
and in chemical bonds.
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Internal energy (E)

Total energy of the system
comprises two components:
- kinetic energy (associated with
various types of molecular motion
and movement of molecules)
- potential energy (associated with
the attractive and repulsive forces
within atoms or molecules)
It is sum of the total kinetic and
potential energy of the system
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Unit of Energy
From kinetic energy has units of kg m
2
s
2

SI unit is Joule (J)
1 J = 1 kg m
2
s
2

The calorie (cal) the energy required to raise
the temperature of 1 g of water by 1 C.
1 cal = 4.18 J
1 kcal = 4.18 kJ
Nutritional or dietary Calorie (Cal)
1 Cal = 1 kcal = 4.18 kJ
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Pressure volume work
Chemical reaction are often accompanied by
volume changes e.g. evolution of gas
Work is done against the surroundings
Reactions are usually done constant pressure
Can we work out how much work is done during
such processes?


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Expansion against a constant
pressure
Consider a gas
confined to a
cylinder with a
movable piston
Area, A
dx
P
ex

System

P

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The work done for a small change

dw = Fdx (classical physics)

Note
negative sign indicates
system is moving
against an opposing
force
system is doing work
and its internal energy
will decrease
The system expands by an
infinitesimal amount dx
Piston area, A
Against an external
pressure, P
ex
,
The work done is

dw = P
ex
Adx
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Note

Change in volume is negative in
compression (reduction in volume), dV is
negative
dw is positive indicating that work has
been done on the system
Provided that no other energy changes
occur during the process, E of the
system increases

During the expansion piston sweeps
volume dV (= Adx)

dw = P
ex
dV
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Suppose gas volume changes from V
1

to V
2
against an external pressure P
ex
A = P
ex
AV
V
i
V
f

P
ex

P
V
P
ex

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}
=
2
1
V
V
ex
dV P w
}
=
2
V
V1
ex
dV P
= P
ex
(V
f
V
i
)

= P
ex
AV

The area under the curve represents the
work done by the gas
Examples P-V work:
internal combustion engine of car - expanding
gases are able to drive a piston
lifting-off of rockets and space vehicles (e.g.
space shuttle)
QUIZ #3
A sample of argon of mass 6.56 g
occupies 20 L at 305 K. (i) Calculate the
work done when the gas expands
isothermally against a constant pressure
of 8 kPa until its volume has increased by
3 L. (ii) Calculate the work that would be
done if the same expansion occurred
reversibly.
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Reversible expansion of a gas
Suppose that the gas expands or contracts in
such way that the external pressure equals the
pressure of the gas.
Expansion/compression is said to take place in a
reversible manner
A reversible change is one that proceeds via an
infinitesimal amount and maybe changed to
proceed in the opposite direction by an
infinitesimal opposite action
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Isothermal reversible expansion of a gas
Suppose the gas expansion occurs
reversibly at constant T, then at each
stage
V
nRT
P =
The work done in the process is
}
= =
f
i
V
V
i
f
V
V
nRTln
V
dV
nRT w
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Final pressure,
P
ex

Area = P
ex
AV
V
f

P
ex

Pressure, P
Volume, V
P = nRT/V
Initial pressure, P
V
i

b
a
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Expansion with no opposing force
Free expansion occurs when there is no
opposing force to the expansion e.g. gas
expands into a vacuum, where P
ex
= 0 (and
therefore dw = 0).
No work is done in the free expansion of a gas.
Open valve
A
B
A
B
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First Law of
Thermodynamics
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Law on the conservation of energy

The law states that energy can neither
be created nor destroyed.
It can only be transformed from one form
into another or redistributed.
The law is summarised in

E = q + w 1
st
Law
Conservation of Energy
37
Consider an example
system of a piston and
cylinder with an
enclosed gas
characterized by
P,V,T & n.
What happens to
the gas if the piston
is moved inwards?
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If the container is insulated the temperature
will rise, the atoms move faster and the
pressure rises.
Is there more internal energy in the gas?
External agent did work in pushing the
piston in ward, w =PAV
Work done on the gas equals the change in
the gases internal energy, w = AE




39
Lets change the
situation:
Keep the piston fixed at
its original location.
Place the cylinder on a
hot plate.
What happens to gas?
40
Heat flows into the gas.
Atoms move faster,
internal energy increases.
q = heat in Joules
AE = change in internal
energy in Joules.
q = AE
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1
st
Law of TD
What if we
added heat and
pushed the
piston in at the
same time?
F
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1
st
Law of TD
Work is done on the
gas, heat is added
to the gas and the
internal energy of
the gas increases!
AE = q + w
F
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System energy heat and work
Energy is defined as the capacity to do work
Work is done on an isolated system increases the
energy of the system (e.g. , compression or winding)
When the system does work on the surroundings, its
energy is reduced (e.g. piston moving out)
The energy of the system with increase or decrease due
to inflow or outflow of heat
The energy of system changes due to energy
entering or leaving in form of heat or work
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Summary E, w, q and the system
More energy enters than leaves, E > 0
More energy leaves than enters, E < 0
Sign convention
w
+ w
q
+ q
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Problem to consider?
An ideal monoatomic gas is
expanded at 298 K from an initial
pressure of 5 atm to a final
pressure of 1 atm isothermally and
reversibly. Calculate the heat
absorbed by the gas (q), work
done on the gas (w) and the
change in internal energy (E).
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Solution
Since the process is taking place
isothermally and at constant pressure,
T
1
= T
2
, T = 0 and E = 0.
From the first law of thermodynamics,
E = q + w
But E = 0, therefore q = w
1
1 1
2
1
mol J 3990
ln5 K 298 x mol K J 8.314
P
P
RTln w

=
=
=
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But since E = 0, q = w
q = w = 3990 J mol
1
Done!
House Keeping!!!
Tutorials
Tuesday 10 11
Friday 9 10
Test 1 Date
Assignment 1 out
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Some thermodynamic conditions
Isochoric
Isobaric
Isothermal
Adiabatic
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Constant pressure and constant
volume process
Typical example chemical reaction in
a sealed vessel to contain any gaseous
products, e.g. a bomb calorimeter

E = q + w



- If work is done by the system then
- w = P
ex
AV
- Thus, AE = q + ( P
ex
AV)
- For a constant volume process
AV = 0, therefore AE = q
v
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The result shows that at constant volume the
heat evolved is a measure of the change in
internal energy
q
v
is used to indicate that heat involved is at
constant volume
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Heat Capacity

A measure of the heat change experienced by a
substance when there is flow of heat
Defined as the quantity of thermal energy
required to raise its temperature by 1 K (or C)
dT
dq
C=
- heat capacity of 1 mol of a substance molar
heat capacity
- heat capacity of 1 gram of a substance -
Specific heat i.e. amount of thermal energy
to raise the temperature of a 1 g substance by
1 degree.
53
Heat transfer metal-water
54
Another expression
dT
dE
dT
dq
C
V
V
= =
Heat capacity at constant volume
55
Heat required (q) = mass x heat capacity x T
= 50 g x 0.90 J g
-1
C
-1
x 53 C
= +2.8 J
Note the + sign indicating that the process is
endothermic
56
Constant pressure processes
Most of our laboratory experiments are at
constant pressure i.e. atmospheric pressure
Volume changes do occur during reactions e.g.
open beakers, flask etc
Some PV work is done
Change is internal energy is

E = q
p
+ (PV)
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Rearranging
q
p
= E + PV
The energy gained or lost during a change
taking place at constant pressure is known as
enthalpy (H)

q
p
= H at constant pressure
We can therefore write that
H = E + PV
The enthalpy change (H) is the change in
internal energy plus the PV work done.
58
Consider a gas that behaves in an ideal manner.
We can write
P
nRT
V =
|
|
.
|

\
|
=
p
nRT
V
At constant T and P

|
.
|

\
|
=
P
RT
n V
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RT n E H
gas
+ =
Change in enthalpy for a reaction that
produces or consumes gas
n
g
is the change in amount of gas.
The change in volume for the reaction
is essentially a change in number of
moles of the species
The heat capacity at constant pressure
is given by

dT
dH
dT
dq
C
P
P
= =
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Variation of enthalpy with temperature
Enthalpy increases as T is raised
Relationship between H and T depends on the
conditions e.g. constant P or V
If the heat capacity is constant over a range of
temperature then
H= C
p
T

In practical terms q
p
=C
p
T i.e. heat
supplied at constant P.

61
- The slope of the tangent of a
curve of H against T at const. P is
the constant-pressure heat
capacity
- Note that the slope may change
with temperature implying that
the heat capacity varies with T.
- Heat capacities at A and B are
different.
Also note the plot for H is steeper
than that for internal energy
62
To calculate the change in enthalpy when C
p

varies with T
Heat substance from an initial temperature T
1
to
a temperature T
2
, the enthalpy change from
H(T
1
) to H(T
2
)

}
+ =
2
1
T
T
P 1 2
dT C ) H(T ) H(T
Assumes that no phase transition occurred
between the two temperatures of interests T
1
and
T
2

63
Kirchoffs law
represents the standard enthalpies of
reaction
}
A + A = A

2
1
) ( ) (
1 2
T
T
P rxn
dT C T H T H
rxn rxn

A
rxn
H

A
rxn
H
Convenient approximate empirical expression
for C
p
is
2
P
T
c
bT a C + + =
a, b and c are independent of temperature
64
Hesss Law
Enthalpy change for a reaction to form
products is the same whether the reactions
takes place in a single step or in a series of
steps.
Law on conservation of energy
A
D
B C
AH
1

AH
2

AH
3

AH
overall enthalpy change is
given as a sum of enthalpies
in the alternate route i.e.
AH = AH
1
+ AH
2
+ AH
3
65
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Significance

Hesss law enables us calculate
different types of heat changes
Enthalpies for reactions that are
difficult or two dangerous to perform
in laboratory can be calculated using
tabulated thermochemical data
Enthalpies of reaction for many
chemical reactions have been
determined that can be used to carry
out various calculations
67
Standard enthalpy changes
Chemist carryout experiments under a variety of
conditions.
Hesss law has one restriction that all the
enthalpies must be measured at the same
temperature and pressure.
Changes in enthalpy are normally reported for
processes taking place under a set of standard
conditions.
The standard state of a substance at a specified
temperature is its pure form at 1 bar e.g.
H
2
O(l) H
2
O(g)
vap
H(373 K) = +40.66 kJ mol
-1

68
(a) Enthalpy of physical change
Standard enthalpy change that accompanies
a change of physical state is called the
standard enthalpy of transition denoted

trs
H e.g.
Standard enthalpy of vaporization,
vap
H
Standard enthalpy of fusion,
fus
H



(b) Enthalpy of chemical change
Standard enthalpy change that accompanies
a chemical reaction
H is the change in enthalpy when reactants
in their standard states change to products in
their standard states


69
It is the difference between the enthalpies of the
reactants and products
AH = Sum of enthalpies products Sum of enthalpies of
reactants
AH = H(products) - H(reactants)
Consider the reaction
aA + bB cC + dD
The standard enthalpy is

(B) bH (A) aH (D) dH (C) cH H
o
m
o
m
o
m
0
m
o
R
+ + =
) (J H
o
m
A
is the standard molar enthalpy of the
species J at the temperature of interest
70
Bond enthalpy and mean bond enthalpy
Enthalpy change related the formation and
breaking of chemical bonds
Energy is required (endothermic) to break bonds
whilst energy is given off (exothermic) in the
formation of bonds
Allows us to predict the likely energy change in a
chemical reaction
Bond dissociation energy is defined as the
amount of energy required to break one mole of
covalent bonds in gaseous species e.g.

CO
2
(g) C(g) + 2O(g) H = 1609 kJ
71
Typical average bond energies
Type of Bond H
d
/kJ mol
1
Molecule
N H 389 NH
3
, ammonia
O H 464 H
2
O, water
C H 413 many organic compounds
C C 346 many organic compounds

The enthalpy change measured during a
chemical reaction is the energy needed to break
all the bonds e.g. combustion of methane, CH
4

CH
4
+ 2O
2
2H
2
O + CO
2
+1646 kJ mol
-1

72
There are four C-H bonds in the molecule
Successive breaking of the bonds gives different
enthalpy change

There are four C-H bonds in the molecule
Successive breaking of the bonds gives different
enthalpy change

CH
4
(g) CH
3
(g) + H(g) H
d
= +427 kJ mol
-1

CH
3
(g) CH
2
(g) + H(g) H
d
= +371 kJ mol
-1


73
The enthalpy change for a chemical reaction can
be calculated using bond dissociation enthalpies
It is the difference between energy required to
break bonds and that released in the formation
of new ones

= s) BE(product ts) BE(reactan H
rxn