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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

V

m3

U

Joules (J)

H

Joules (J)

S

Joules/Kelvin (J /
K)

G

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

32 kPa.reported at 298. .15 K and 101.

The First Law of Thermodynamics 1st Law for a closed system 1st Law for an open system .

It is written differential form dU = dQ . 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. the temperature and pressure increase and some heat will be transferred out of the system.dW integrated form (1) The sign conventions for heat transfer and work are . it does work on the surroundings and the temperature and pressure decrease. As a real gas expands. Only heat and work are transferred to the system as shown in the animation above.A closed system is one where no material is transferred across the system boundaries. As work is done on a real gas.

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. values at the start and end of the irreversible process are required to calculate the change in internal energy. . 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.

where it cools down and the pressure decreases. 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 first law written for an open system. During the expansion process work is extracted from the gas. In the process shown above. as well as heat and work. The gas then passes through an expansion turbine. because the enthalpy includes the PV work done on the system by the gas .The First Law of Thermodynamics for an Open System An open system is one where material can flow across the boundaries of the system. gas is entering the system and being heated in the heat exchanger where its temperature pressure and volume increase. 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.

flowing in and the PV work done by the system as the gas flows out. . 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 reversible. 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.

No heat transfer to the system .Constant Temperature Adiabatic .Isochoric .Constant Volume Isobaric .Constant Pressure Isothermal .

Work done and Heat Transferred Applying the first law of thermodynamics to the process 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 .dW Replacing dW with the reversible work dU = dQ .

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 .For a constant volume process.

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

and substitute into the first law dH .VdP = dQ . 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 .PdV the PdV terms cancel out and since pressure is constant dP = 0. heat is added or removed and the temperature and volume change.PdV . 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.

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the internal energy is a function of temperature only. then dU is zero and dQ = dW = PdV using the ideal gas law and integrating between the start and end of the process . the temperature is constant. Applying the first law of thermodynamics to this closed process For an ideal gas. and since the temperature is constant.Isothermal Expansion and Compression Work Done and Heat Transferred In an isothermal process.

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. 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.PdV dU is zero because the process is isothermal and the working fluid is an ideal gas. dU = TdS . the same amount of energy will appear as heat transferred from the gas as it is compressed. Note that as the gas is compressed heat is given out and that as it expands heat is absorbed. Entropy Change The Entropy change comes from the equation which incorparates the first and second laws.This equation tells us that if we do some work on a gas to compress it. .

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.Work done and Heat Transferred Applying the first law of thermodynamics to the process dU = dQ . for an ideal gas .dW since no heat is transferred dQ=0 and dU = .

integrating between the start and end of the process and or using the ideal gas law to replace V These equations relate P.This is done because the ratio of specific heats does not vary with 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 .V and T at the start of the process to P. the work done is calculated from For an adiabatic process. When the temperatures at the start and end of the process are known.V and T at the end of the process. the work done on or by the gas causes the temperature.

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 .

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Answers for Tutorial Sheet 2 Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9 Q10 Q11 Q12 Q13 Q14 .