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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!

Basic Physical Chemistry - Thermodynamics

Thermodynamic Surroundings
Thermodynamic surroundings are defined as
everything other than the thermodynamic
system. In other words, the entire rest of the
Universe.

Basic Physical Chemistry - Thermodynamics

The Universe
The Universe is therefore the system plus its
surroundings.

Basic Physical Chemistry - Thermodynamics

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.
Basic Physical Chemistry - Thermodynamics

Image: Nikthestunned

Thermodynamic Surroundings
Fe2O3 + 2Al 2Fe + Al2O3

Basic Physical Chemistry - Thermodynamics

Image: NASA / ESA

Thermodynamic Surroundings

super nova

Basic Physical Chemistry - Thermodynamics

Thermodynamic Surroundings
Surroundings are assumed infinite and remain at
constant temperature and pressure.
The vast size of the Universe validates this
assumption.

Basic Physical Chemistry - Thermodynamics

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.

Basic Physical Chemistry - Thermodynamics

Open, Closed and Isolated


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

Open
Basic Physical Chemistry - Thermodynamics

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Open, Closed and Isolated


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

Closed
Basic Physical Chemistry - Thermodynamics

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Open, Closed and Isolated


An isolated system may exchange neither
energy nor matter with its surroundings.

Isolated
Basic Physical Chemistry - Thermodynamics

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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
Basic Physical Chemistry - Thermodynamics

Hot

Cold

Adiabatic
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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?
Basic Physical Chemistry - Thermodynamics

14

Isothermal, Isobaric and Isochoric


Isothermal implies constant temperature, T.
Isobaric implies constant pressure, p.
Isochoric implies constant volume, V.

Basic Physical Chemistry - Thermodynamics

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
Basic Physical Chemistry - Thermodynamics

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

Basic Physical Chemistry - Thermodynamics

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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

Basic Physical Chemistry - Thermodynamics

Work energy transfer is


uniform molecular motion

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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
Basic Physical Chemistry - Thermodynamics

19

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0th Law of Thermodynamics


Temperature

Basic Physical Chemistry - Thermodynamics

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.

Basic Physical Chemistry - Thermodynamics

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.

Basic Physical Chemistry - Thermodynamics

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.

Basic Physical Chemistry - Thermodynamics

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


Basic Physical Chemistry - Thermodynamics

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.
Basic Physical Chemistry - Thermodynamics

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.
Basic Physical Chemistry - Thermodynamics

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1st Law of Thermodynamics


Enthalpy

Basic Physical Chemistry - Thermodynamics

The First Law of Thermodynamics


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

Basic Physical Chemistry - Thermodynamics

[1]

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


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
Basic Physical Chemistry - Thermodynamics

[2]
4

The First Law of Thermodynamics


DU = qin + won

[1]

won = pDV

[2]

DU = qin pDV
Expansion work clearly depends on p and DV.

Basic Physical Chemistry - Thermodynamics

Image: NASA

Free Expansion
DU = qin pDV
But in space p = 0
DU = qin

Basic Physical Chemistry - Thermodynamics

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

Basic Physical Chemistry - Thermodynamics

[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]
Basic Physical Chemistry - Thermodynamics

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Reversible Isothermal
Expansion of an Ideal Gas

Basic Physical Chemistry - Thermodynamics

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

Basic Physical Chemistry - Thermodynamics

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.
Basic Physical Chemistry - Thermodynamics

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?
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

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Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

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Isothermal Expansion
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
Basic Physical Chemistry - Thermodynamics

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
Basic Physical Chemistry - Thermodynamics

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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

won for Reversible Isothermal Expansion


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

won for Reversible Isothermal Expansion


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.

Basic Physical Chemistry - Thermodynamics

16

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same or similar license to this one.
For any reuse or distribution, you must make clear to others the license terms of this work. The best way
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Heat Capacity

Basic Physical Chemistry - Thermodynamics

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
Basic Physical Chemistry - Thermodynamics

[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.
Basic Physical Chemistry - Thermodynamics

710

130

2010

880

Specific heat capacities of substances / J K1 kg1

2000

440

1340

520

140

390

710

1670

Basic Physical Chemistry - Thermodynamics

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

Basic Physical Chemistry - Thermodynamics

[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.
Basic Physical Chemistry - Thermodynamics

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


Basic Physical Chemistry - Thermodynamics

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