Physical Chemistry Week 1

Thermodynamic Definitions
Basic Physical Chemistry - Thermodynamics
Thermodynamic System
A thermodynamic system is defined as any part
of the Universe under consideration.
It may be something as simple as a beaker of
water or as complicated as an entire galaxy!
Thermodynamic Surroundings
Thermodynamic surroundings are defined as
everything other than the thermodynamic
system. In other words, the entire rest of the
Universe.
The Universe
The Universe is therefore the system plus its
surroundings.
Image: NASA
The Vastness of the Universe
The observable Universe is a sphere with a radius of ca. 4.66 1010 light years.
A light year is 9.46 1015 m. The observable Universe is thus ca. 880 Ym or
880,000,000,000,000,000,000,000,000 m across.
Image: Nikthestunned
Fe2O3 + 2Al 2Fe + Al2O3
Image: NASA / ESA
super nova
Surroundings are assumed infinite and remain at
constant temperature and pressure.
The vast size of the Universe validates this
assumption.
Boundary Conditions
The boundary may be actual or notional.
It controls transfer of work, heat and matter from
the system to the surroundings and vice-versa.
The boundary may or may not impose
restrictions on such transfers.
Open, Closed and Isolated

An open system may exchange both energy and
matter with its surroundings.
Open
10

A closed system may exchange energy but not
matter with its surroundings.
Closed
11

An isolated system may exchange neither
energy nor matter with its surroundings.
Isolated
12
Diathermic and Adiabatic

A diathermic system allows heat flow into or out
of the system.
An adiabatic system prevents heat flow into or
out of the system.
Hot
Cold
Diathermic
Hot
Cold
Adiabatic
13
Diathermic and Adiabatic Walls

Both containers are attempts
to create adiabatic walls. The
flask is a good approximation
to an adiabatic calorimeter
the cardboard cup isnt
Which will keep coffee
warmer for longer?
14
Isothermal, Isobaric and Isochoric

Isothermal implies constant temperature, T.
Isobaric implies constant pressure, p.
Isochoric implies constant volume, V.
15
State functions
A state function describes the state of a system.
The following are all state functions:
Pressure, p
Volume, V
Temperature, T
Mass, m
Quantity, n
Internal Energy, U
Enthalpy, H
Entropy, S
Gibbs Energy, G
16
Path functions
A state function describes the current state of a
system.
How the system came to be in that particular
state is of no consequence.
Functions governing transition between states
are called path functions.
Heat, q
Work, w
17
Heat and Work

The state of a system is changed by the supply
or removal of energy in the form of heat or work.
Heat energy transfer is

random molecular motion
Work energy transfer is

uniform molecular motion
18
Heat and Work Conventions

Path functions are positive when energy enters
the system.
Path functions are negative when energy leaves
the system.
They are often defined as:

heat supplied to the system, qin
mechanical work done on the system, won
19
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0th Law of Thermodynamics

Temperature
The First Law of Thermodynamics

Developed around 1850 by Rudolf Clausius.
Adaptation of the Law of Conservation of Energy
for thermodynamic systems.
Defined thermodynamic energy or internal
energy for a thermodynamic system.
Concerns energy changes and lead to the
definition of a new state function called enthalpy.
The Second Law of Thermodynamics

Also developed around 1850 by Rudolf Clausius
following initial work by Sadi Carnot in 1824.
Describes the direction in which all processes
spontaneously occur, e.g. a hot object loses heat
to its surroundings.
Lead to the definition of a new state function
called entropy which fundamentally measures
disorder.
3rd Law of Thermodynamics

Developed in 1912 by Walter Nernst.
Considers the entropy of perfect crystals.
Lead to the definition of zero on the entropy
scale thus enabling determination of absolute
entropy.
A Crisis of Temperature
Temperature, which lay at the heart of this new
science of thermodynamics, was routinely
measured by thermometer.
Think how a thermometer works

The Zeroth Law of Thermodynamics

When two objects are separately in
thermodynamic equilibrium with a third object,
they are in thermodynamic equilibrium with each
other.
Whenever two objects are in contact with one
another energy will flow between them until they
reach a state of thermodynamic equilibrium.
Upon reaching this state we say that the two
objects are at the same temperature.
The Zeroth Law of Thermodynamics

When two objects are separately at the same
temperature as a third object, they are at the
same temperature as each other.
This sounds obvious but it has vital ramifications
for the measurement of temperature by
thermometer.
The obvious nature of this statement explains
why it did not become a law of thermodynamics
until well after the other three laws.

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1st Law of Thermodynamics

Enthalpy

Stated by Rudolph Clausius in 1850.
Energy can neither be created nor destroyed,

merely changed from one form into another.
Every system possesses an internal energy, U.
DU = qin + won
[1]
Evolution of Gas from a Reaction
Zn (s) + 2HCl (aq) ZnCl2 (aq) + H2 (g)
The Work Done by an Expanding Gas

w = Fd
Cross-section, A
p=F/A
Expanding
Gas
\ F = pA
External
Pressure, p
\ w = pAd
w = pDV
Frictionless piston moves through a distance d
won = pDV
[2]
4

DU = qin + won
[1]
won = pDV
[2]
DU = qin pDV
Expansion work clearly depends on p and DV.
Image: NASA
Free Expansion
DU = qin pDV
But in space p = 0
DU = qin
However, relatively very

few experiments are
carried out in space!
Image: NYNAS
Reactions at Constant Volume

Constant volume reactors must withstand massive
pressure changes heavy chemical industry, $.
DU = qin pDV
But at constant volume DV = 0

DU = qv
[3]
Image: Lilly M
Reactions at Constant Pressure

DU = qin pDV
\ DU + pDV = qin at contant pressure
Now we define a new state function, enthalpy:
H = U + pV
d uv
dv
du
Product rule:
=u
+v
\ DH = DU + D(pV)
dx
dx
dx
DH = DU + pDV + VDp
But, at constant pressure, Dp = 0 hence VDp = 0
\ DH = DU + pDV
DH = qp
[4]

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Reversible Isothermal
Expansion of an Ideal Gas
The Ideal Gas Equation

pV = nRT
p is pressure
V is volume
n is quantity
R is the ideal gas constant, 8.314 J K1 mol1
T is absolute temperature
The Ideal Gas Equation

p = nRT / V
Consider 1 mol of an ideal gas at 298 K
p = 1 mol 8.314 J K1 mol1 298 K / V

p = 2477.572 J / V
Using the above equation, calculate the pressure
of the gas for volumes of 1, 3, 5, 7, 9 and 11 m3.
Answer: 2478, 826, 496, 354, 275 and 225 Pa
respectively.
Isothermal Expansion
One mole of
Gas
External
Pressure, p
Ambient temperature = 298 K
External pressure, p = 2478 Pa volume = 1m3

Now imagine the external pressure suddenly drops
to 826 Pa. What happens to the gas?
2500
2000
p / Pa
1500
wtotal = 1652 + 982 + 708 + 550 + 450 J = 4342 J

1000
500
0
1.00
w = pDV
826 Pa 2 m3
w = 1652 J
2.00
w = pDV
496 Pa 2m3
w = 982 J
3.00
4.00
w = 708 J
5.00
6.00
w = 550 J
7.00
8.00
w = 450 J
9.00
10.00
11.00
V / m3
2500
2000
p / Pa
1500
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
2500
2000
p / Pa
1500
p = nRT / V
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
2500
2000
1500
p / Pa
won = 4342 J
1000
500
w = 1652 J
w = 982 J
0
1.00
2.00
3.00
4.00
w = 708 J
5.00
6.00
w = 550 J
7.00
8.00
w = 450 J
9.00
10.00
11.00
V / m3
2500
2000
1500
p / Pa
won = 5004 J
1000
500
1239 J
826 J
619 J
0
1.00
2.00
3.00
496 J
4.00
413 J
5.00
354 J
6.00
310 J
7.00
275 J
8.00
248 J
9.00
225 J
10.00
11.00
V / m3
2500
2000
1500
p / Pa
won = 5428 J
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
10
2500
2000
1500
p / Pa
won = 5672 J
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
11
2500
2000
1500
p / Pa
won = 5803 J
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
12
Reversible Isothermal Expansion

2500
2000
1500
p / Pa
won = 5941 J
1000
500
0
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
V / m3
13
won for Reversible Isothermal Expansion

won = pdV
But, pV = nRT
So, p = nRT / V
won = (nRT / V) dV
Now consider an expansion from Vi to Vf

Vf
won = nRT
dV
V
Vi
14

Vf
won = nRT
dV
V
dx
= lnx + c
x
Vi
won = nRT lnV
Vf
Vi
won = nRT(lnVf lnVi)

Vf
won = nRT ln
Vi
lnA lnB = ln
A
B
[5]
15

Vf
won = nRT ln
Vi
won = 1 mol 8.314 J K1 mol1 298 K ln(11)
won = 5941 J
Reversible change is a theoretical construct.

Determines maximum possible expansion work.
16

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Heat Capacity
Heating Objects
Low
Heat
Capacity
High
Heat
Capacity
Heat Capacity, C, is the heat energy required to

raise the temperature of an object by 1 C or 1 K.
C = q / DT
[6]
2
Definitions of Heat Capacity

Heat capacity is an extensive property.
Specific Heat Capacity, Cs = C / m units J K1 kg1

Molar Heat Capacity, Cm = C / n units J K1 mol1
Specific Heat capacity and Molar Heat Capacity
are intensive properties.
710
130
2010
880
Specific heat capacities of substances / J K1 kg1
2000
440
1340
520
140
390
710
1670
Isochoric and Isobaric Heat Capacities

Isochoric heat capacity is defined as:
CV = qV / DT = DU / DT
[7]
Isobaric heat capacity is defined as:

Cp = qp / DT = DH / DT
[8]
Cp,m & CV,m Relationship for an Ideal Gas

H = U + pV
Hm = Um + pVm
For an ideal gas: pV = nRT
pVm = RT
Hm = Um + RT
RT = 8.314 J K1 mol1 298 K ~ 2.5 kJ mol1
This is not negligible for a gas.
Cp,m & CV,m Relationship for an Ideal Gas

Hm = Um + RT
For a change of temperature DT
DHm = DUm + RDT
DHm DUm
=
+R
DT
DT
Cp,m = CV,m + R
[9]
where R = 8.314 J K1 mol1


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Thermodynamic Definitions

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

The Vastness of the Universe

Basic Physical Chemistry - Thermodynamics

Image: NASA / ESA

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

Open, Closed and Isolated

Open, Closed and Isolated

Open, Closed and Isolated

Diathermic and Adiabatic

Diathermic and Adiabatic Walls

Isothermal, Isobaric and Isochoric

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

Heat and Work

Heat energy transfer is

Basic Physical Chemistry - Thermodynamics

Work energy transfer is

Heat and Work Conventions

They are often defined as:

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0th Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

The First Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

The Second Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

3rd Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

Think how a thermometer works

The Zeroth Law of Thermodynamics

The Zeroth Law of Thermodynamics

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1st Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

The First Law of Thermodynamics

Energy can neither be created nor destroyed,

Basic Physical Chemistry - Thermodynamics

Evolution of Gas from a Reaction

Zn (s) + 2HCl (aq) ZnCl2 (aq) + H2 (g)

Basic Physical Chemistry - Thermodynamics

The Work Done by an Expanding Gas

Frictionless piston moves through a distance d

The First Law of Thermodynamics

Basic Physical Chemistry - Thermodynamics

Basic Physical Chemistry - Thermodynamics

However, relatively very

Reactions at Constant Volume

But at constant volume DV = 0

Basic Physical Chemistry - Thermodynamics

Reactions at Constant Pressure

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Basic Physical Chemistry - Thermodynamics

The Ideal Gas Equation

Basic Physical Chemistry - Thermodynamics

The Ideal Gas Equation