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Chemical Engineering Thermodynamics

Definitions of Basic Quantities


The First Law of Thermodynamics
The Second Law of Thermodynamics
Reversible Processes for an Ideal Gas
PVT Properties of Gases and Liquids
Ideal Phase Equilibria
Ideal Gas Phase Reaction Equilibria
Tutorial Sheet 1 Answers
Tutorial Sheet 2 Answers

Extensive State Properties


Extensive state properties are those whose value does not depend
on the amount of a particular substance that is present. There are
two of them
Property
Temperature
Pressure

Symbol
T
P

S.I. Unit
Kelvin (K)
Pascals (Pa)

Intensive State Properties


Intensive state properties are those whose values depends on the
amount of substance. The ones you will commonly meet are
Property

Definition
Volume of a
Volume
substance
The translational,
rotational and
Internal Energy vibrational kinetic
energy of a
substance
Enthalpy
U + PV
The entropy is a
measure of the
lack of structure or
Entropy
the amount of
disorder in a
system
Gibbs free energy
H - TS

Symbol

S.I.Unit

m3

Joules (J)

Joules (J)

Joules/Kelvin (J /
K)

Joules (J)

Standard States
If the temperature and pressure of a pure substance are known then
its thermodynamic state is defined. So that measured
thermodynamic data can be compared, standard values of the

temperature and pressure have been agreed internationally.


The standard pressure is 101.32 kPa. This is written

The standard state of a substance is then its state at this pressure


Gas: Ideal Gas at 101.32 kPa
Liquid: Pure liquid at 101.32 kPa
Solid: solid in its most stable crystal structure at 101.32 kPa

Enthalpy
The temperature that is most often used for recording
thermodynamic data is 298.15 K, and by international convention
the enthalpy of a pure element at 298.15 K and standard pressure is
zero.

For compounds, the heat of formation at 298.15 K represents the


value of the enthalpy for that compound at 298.15 K.
More often than not, heats of reaction are also given at 298.15 K

Internal energy
Since the enthalpy has been set to zero at 298.15 K then the intenal
energy at standrd pressure and 298.15 K is calculated from the
definition of enthalpy

Entropy
The entropy has a standard that is fixed by the Third Law of
Thermodynamics. This states that for a pure substance, the entropy
of the substance at standard pressure and zero K is zero

Gibbs Free Energy


The enthalpy of an element has an internationally defined value at
298.15 K and 101.32 kPa. The entropy is zero at 0 K and 101.32
kPa.
Therefore values of the Gibbs Free energy for an element at any
temperature T, can be calculated using the definition of the Gibbs
free energy.

In the same way that the value of the enthalpy for a compound was
found from the heat of formation, the Gibbs free energy of a
compound can be found by working out the Gibbs free energy
change for the reaction where it is formed from its elements.
The Gibbs free energy change for reactions are most frequently

reported at 298.15 K and 101.32 kPa.

The First Law of Thermodynamics


1st Law for a closed system
1st Law for an open system

A closed system is one where no material is transferred across the


system boundaries. Only heat and work are transferred to the
system as shown in the animation above.
As work is done on a real gas, the temperature and pressure
increase and some heat will be transferred out of the system.
As a real gas expands, it does work on the surroundings and the
temperature and pressure decrease. Heat is transferred to the
system.
We balance the changes in the internal energy of the gas with the
amount of heat transferred to/from the gas and work done by/on
the gas. This energy balance is called the first law for a closed
system. It is written
differential form dU = dQ - dW
integrated form

(1)

The sign conventions for heat transfer and work are

Heat transferred to the system is POSITIVE


Work done on the system is NEGATIVE

If the processes by which heat is transferred or work done on/by


the system are reversible, then we can calculate numerical values
of for the Q and W in equation (1) and work out the internal energy
change.
If the processes by which heat is transferred or work done on/by
the system are irreversible then, values at the start and end of the
irreversible process are required to calculate the change in internal
energy.

The First Law of Thermodynamics for an Open System

An open system is one where material can flow across the boundaries of the
system, as well as heat and work.
In the process shown above, gas is entering the system and being heated in
the heat exchanger where its temperature pressure and volume increase. The
gas then passes through an expansion turbine, where it cools down and the
pressure decreases. During the expansion process work is extracted from
the gas.
The first law written for an open system, with the assumption that the
potential and kinetic energy of the gas are the same at the inlet and out is
(1)

Where
is the enthalpy flowing in through the dotted boundary line and
is the enthalpy flowing out through the dotted boundary line. The sign
conventions are:
Heat transferred to the system is POSITIVE
Work done on the system is NEGATIVE

The first law for a flow process is written in terms of the enthalpy H,
because the enthalpy includes the PV work done on the system by the gas

flowing in and the PV work done by the system as the gas flows out.
If the processes by which heat is transferred or work done on/by the system
are reversible, then it is possible to calculate numerical values of for the Q
and W in equation (1) and work out the internal energy change.
If the processes by which heat is transferred or work done on/by the system
are irreversible then, values at the start and end of the irreversible process
are required to calculate the change in internal energy.

Isochoric - Constant Volume


Isobaric - Constant Pressure
Isothermal - Constant Temperature
Adiabatic - No heat transfer to the system

Work done and Heat Transferred


Applying the first law of thermodynamics to the process
dU = dQ - dW
Replacing dW with the reversible work
dU = dQ - PdV
since the volume is constant dV = 0 and
dU = dQ
using the definition of the specific heat at constant volume

to replace dU in the first law

For a constant volume process, the addition or removal of heat will


lead to a change in the temperature and pressure of the gas, as
shown on the two graphs above
Entropy Change
To find the Entropy change, start with the expression derived from
the first law
dU = dQ
and replace dU using the definition of specific heat at constant
volume and dQ using the definition of entropy

Work done and Heat Transferred


Applying the first law of thermodynamics to the process
dU = dQ - dW
Replacing dW with the reversible work
dU = dQ - PdV
The volume will change as the gas is heated at constant pressure.
To make calculations more straight forward, use ENTHALPY, H
H = U + PV
dH = dU + PdV + VdP
rearrange for dU
dU = dH - PdV - VdP

and substitute into the first law


dH - PdV - VdP = dQ - PdV
the PdV terms cancel out and since pressure is constant dP = 0, so
that
dH = dQ
The definition of the specific heat at constant pressure

is used to replace dH in the first law

During a constant pressure process, heat is added or removed and


the temperature and volume change. The volume at the end of the
process can be found using the ideal gas law and the work
calculated from

Entropy Change
Starting with the first law expression for the process
dH = dQ
and replacing dH from the definition of specific heat at constant
pressure and Dq from the definition of entropy

Isothermal Expansion and Compression

Work Done and Heat Transferred


In an isothermal process, the temperature is constant. Applying the
first law of thermodynamics to this closed process

For an ideal gas, the internal energy is a function of temperature


only, and since the temperature is constant, then dU is zero and
dQ = dW = PdV
using the ideal gas law and integrating between the start and end of
the process

This equation tells us that if we do some work on a gas to compress


it, the same amount of energy will appear as heat transferred from
the gas as it is compressed.
Entropy Change
The Entropy change comes from the equation which incorparates
the first and second laws. The energy balance is the first law, and
the heat transfer is expressed as an entropy change which is a
statement of the second law.
dU = TdS - PdV
dU is zero because the process is isothermal and the working fluid
is an ideal gas, so that
TdS = PdV
substituting for the pressure from the ideal gas law for the pressure

and finally integrating between the start and end of the process

Isothermal compression is shown above on P-V and T-S diagrams.


Note that as the gas is compressed heat is given out and that as it
expands heat is absorbed.

Work done and Heat Transferred


Applying the first law of thermodynamics to the process
dU = dQ - dW
since no heat is transferred dQ=0 and
dU = - dW
replacing dW with the reversible work term and dU from the
definition of specific heat at constant volume

is replaced using the relationship between the specific heat at


constant pressure and the specific heat at constant volume, for an
ideal gas

This is done because the ratio of specific heats does not vary with
temperature.

integrating between the start and end of the process

and

or using the ideal gas law to replace V


These equations relate P,V and T at the start of the process to P,V
and T at the end of the process. When the temperatures at the start
and end of the process are known, the work done is calculated from

For an adiabatic process, the work done on or by the gas causes the
temperature, pressure and volume to vary as shown in the graphs
above
Entropy Change
There is no heat transfer to or from the gas and the process is
reversible so that

PVT Properties of Gases and Liquids

P-T and P-V Behaviour


Virial Equation of State
Compressibility Factor
Cubic Equations of State

Answers for Tutorial Sheet 1


Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9 Q10 Q11 Q12 Q13 Q14

Answers for Tutorial Sheet 2


Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9 Q10 Q11 Q12 Q13 Q14