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Faculty of Engineering & Physical Sciences

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Department of Chemical & Process Engineering

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Please tick: [ ] Chemical Engineering [ ] Civil Engineering

Student Name: Christian Dawit URN: 6521798

Module Code & Title: Chemical thermodynamics and Applied thermodynamics ENG2122

Assignment/Lab Title: Final Assessment Coursework

Person Responsible for Marking: Esat Alpay and Ralph Chadeesingh

Signature: Date: 26/05/20

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A1

i)
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ii)
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A2
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A3
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B1.
i) The pressure and temperature effects on reaction equilibria, i.e. the
reaction equilibrium constant and conversion.

Question:
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Model answer:
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(ii)The effect of non-ideality (e.g. real-gas behaviour) on reaction equilibria calculations.

Question:
•What is the difference Between an ideal gas and a real gas? Also explain the repercussions
of high pressure and low temperature on real gases.

•Calculate the pressure using the ideal gas equation and Van der Waals equation in which 3
moles of N2 is within a 10 L flask at 20oC where a=1.408 L2atm/mol2 and b= 0.03913 L/mol.

Model Solution:
Ideal Gas Obeys Kinetic molecular theory, in which volume occupied by gas particles would
be insignificant compared to total and there are also no intermolecular forces of attraction or
repulsion occurring. Ideal gases consist of molecules that are constantly in arbitrary motion
linearly. All collisions that occur are perfectly elastic meaning no kinetic energy of molecules
has been lost. Additionally, Pressure exists in containers where collisions between
molecules walls of the container.

Real gas tends to deviate from perfect or ideal gas characteristics, in particular when
pressure is high and temperature is low. In order to measure the degree of deviation from
ideal behaviour we can use the compressibility factor which is Z = PV/RT. Z=1 the gas is in
ideal condition but in reality this is not the case.

At High pressure gas molecules are compacted together in space. Since there more
collisions and crowding gas molecules will endure greater intermolecular forces of attractive.
Additionally, high pressure means that the gad molecules will use up all of the container and
parts the of the container that isn’t occupied of any 1 molecule will have a lesser volume
than the volume in ideal gas conditions. The reduction of the unfilled volume will lead to
pressure increasing above ideal gas conditions.

Low temperature can also cause deviations in perfect gas behaviour. This is because at
lower temperature gases will have lower average kinetic energy. Large amounts gas
molecules will have inadequate levels of kinetic energy to overcome the intermolecular
forces coming from other nearby atoms. As a result, gas molecules with collide with the
container walls less frequently and at a lesser force.
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B2.
Limitations of Compression factor and uses
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Compression factor is an effective property used in thermodynamics to alter the perfect gas
law taking into consideration as to how real gases behave. This is used to measure the
extent of thermodynamics properties of real gases deviates from perfect gases. Ideal gas
equation is an intuitive and commonly used method to use when calculating for pressure or
temperature. Gases deviate massively from rom perfect gas features in the saturation and
critical point. By introducing the correction factor we can accurately look at the deviations
from ideal gas behaviour for a given temperature and pressure using compressibility factor
(Z):
𝑃𝑉
Z=
𝑅𝑇
 P- pressure (Pa)
 V-volume (m3)
 R- universal gas constant (8.314 J mol-1 K-1)
 T- temperature (K)
The major limitation of the equation of state is that Z isn’t a constant, but it differs from gas to
the next alongside a given temperature of a gas which is taken into account. This means that
it is necessary that Z is determined by conducting an experiment. Real gases tend to have
high compressibility so it can it easily be compressed. The uses of high compressible gases
are Liquefied petroleum gas in which a large amount of gas can be contained and
compressed in a cylinder where it’s made up of petroleum gas made from fuel. Another
application for high compressible is the gas used to pump tyres in petrol stations creating
high pressure in the tyres. Perfect gas estimations are normally accurate but this model isn’t
ideal to use when pressure are high and temperatures are low. The ideal gas model also
isn’t effective for gases with high molar masses (heavy gases) and strong inter-molecular
forces like NaCl. The model doesn’t enable for phase transition to occur so it must be
modelled by more difficult and more complicated equation of state.

Limitations of Viral Equation of State and uses

Virial equation of state is a series of polynomials within the density and is unambiguous in
pressure and an equation can be derived using statistical mechanics. It expresses deviation
in terms of a power series shown below. Additionally, these differing coefficients can also
express deviations in terms of perfect gas behaviour and intermolecular functions. These
expressions can mathematically suggest the interactions in collections of a rising number of
molecules.

𝑃
= 𝜌 + 𝐵𝜌2 + 𝐶𝜌3
𝑅𝑇

 B- 2nd virial coefficient

 C- 3rd virial coefficient
The main use of the virial equation of state is the study of medium to low pressure gases
mainly, but this isn’t ideal for liquid. The problem with using the Virial equation of state
appeared when taking into account the behaviour of mixtures, as the system of this
nature may split in a range of diverse compositions. Complex equation does a very good
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job of representing pressure-specific volume-temperature behaviour and ideal to use

computer software applications. But when doing calculation on paper it better to read off
a properties tables or more intuitive EOS. This Is especially correct for specific volume
calculations because all previous equations aren’t explicit in specific volume and a trial
and error method must be conducted.

Limitations of Fugacity and uses

Fugacity measures tendency of parts of a liquid mixture to vaporize from the mixture. The
mole fraction of vapour form isn’t the same as the liquid mixture, its richer in molecules of
that component it’s here it’s more likely to exit from the liquid phase. This isn’t a physical
property of a substance, instead it is fundamentally associated to chemical potential. For a
perfect gas fugacity would be the same as pressure but in reality no substance is can
realistically be perfect under low pressure and high temperature. Hence why fugacity is used
to describe liquids, solids and gases that are not perfect or ideal. This is a function of matter
at unvarying temperatures meaning this only becomes effective for substances part from
perfect gases.
Fugacity shouldn’t be used to substitute pressure in any equation especially EOS (Equation
of state). Fugacity should only strictly be used to appropriately define the chemical potential
equation for a real gas which should be closely similar to the equation pv = nrt which is the
ideal gas equation. Fugacity is very useful in Chemical engineering as you can foresee the
final phase at a wide range of temperatures and pressure where in which conducting test in
laboratory is not required. Additionally, it can be effective when there is multi-component
species involved whether it be a combination solid, liquid and gas in equilibrium, even
though fugacity favours predicting the phase of a singular substance.

C1.
a) Isentropic efficiency of a turbine is defined as the ratio of the output of the actual
work done on the turbine to work output of the turbine if the turbine goes through an
isentropic process amongst the equal inlet and outlet pressures. An isentropic
process in general is an ideal process to use in turbines because adiabatic turbines
tend be in steady-flow process where Q=0 hence it’s an adiabatic process and inlet
and outlet pressures does not vary.

Efficiency is normally defined as a value less than 1 so the equation for isentropic
efficiency is:
wa
ηT =
ws
Wa – work of Actual turbine
Ws – work of the Isentropic turbine
ηT – Efficiency of isentropic turbine

Wa and Ws both be solved via an energy balance around the turbine where kinetic and
potential energies tend to be linked with the process via a turbine. Additionally, the process
is insignificant to enthalpy change.
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irreversibility isn’t involved in isentropic process and is the best process for the adiabatic
turbines.

figure 2.

This an h-s graph illustrating what goes on within an adiabatic turbine.

In industry very developed turbines primarily have isentropic efficiency of at least 90%. However, for
smaller turbines they tend to have an efficiency less than 70%.

Isentropic work is the optimum output of work an adiabatic turbine can realistically produce. This
means that isentropic work will be greater than actual work. To determine the isentropic efficiency
using the h-s graph the equation is:

h1 −h2a
ηT =
h1 −h2s

b)

Rankine cycle for P-v

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T-s diagram

4 processes are involved in the Rankine cycle in which irreversibility’s are not involved:

o 1 to 2 – Adiabatic and reversible (isentropic) to compression

The centrifugal pump adiabatically compresses the condensed liquid. The condensed
liquid is then pumped in to a boiler under high pressure where work is done on the
fluid. This increases the enthalpy. However, entropy will always be fixed so it
remains unchanged.

o 2 to 3 – addition of heat under constant pressure- liquid condensate coming from a

peripheral source undergoes heat transfer at high-pressure. The water feed is
heated and reaches the boiling point ad then its evaporated in the boiler.

o 3 to 4 – Adiabatic and reversible (isentropic) expansion in a turbine - Steam expands

adiabatically in the steam turbine so work is produced which then liquidated to the
condenser even though it is not fully condensed. Work is done on the surroundings
coming from steam and loses energy released equal to the work that exits the
system.

o 4 to 1 – excess heat removed by the cooling tower (heat rejection) under constant
pressure- partially condensed steam rejects heat in which the process is completed
under constant pressure. Heat transfer occurs from the vapour to cooled water
flowing in cooling circuit. The vapour condenses and the cooling water gains heat
meaning the temperature of the cooled water increases.
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Reversible and adiabatic turbine sketch

c) According to the 2nd law of efficiency there is no process can realistically be isentropic or no
process can use 100% of energy during the process or a system. 2nd law of efficiency is defined as
the measure of the amount of optimum Carnot you can achieve theoretically speaking. It’s
essentially comparing the actual system efficiency to the maximum theoretical efficiency. The idea
of Reversible processes applies to this rule. This allows us to compare the performance of many
devices made to do same task. Therefore, a better a device should lead to a better performance so
the 2nd law efficiency should improve so irreversibility should be lower. Since we assume no heat is
changed from the system where no irreversibility happens within the process reversible processes
can also be seen as an adiabatic process making the process isentropic where entropy is fixed so it
remains constant as entropy change 0. This is because entropy change is equal to heat duty (Q)
divided Temperature, an adiabatic system means Q = 0.

C2.

a) Net Work of output is the difference between work given by steam turbine and work
required by the pump. Work needed by the pump is neglected in steam calculations
because as its very small value to point where it doesn’t impact the Net Work output.
Additionally, it makes up below 1% of the overall turbine power. Steam turbine is
expanded to decrease the pressure of the condenser so network done by the pump will
decrease as a result. Additionally, Water is almost impossible to compress and has a very
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small specific volume to point where its close hence why we ignore pump work in steam

turbine calculations. This can be illustrated using the Rankine cycle T-s diag

Notice that as Temperature falls the Wnet increases

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e) The efficiency is very low meaning that the quality of the steam turbine is really poor and
needs to be improved. In order to improve the efficiency of the turbine the quality of the
steam needs to improve at the exhaust turbine. Additionally, the input heat should be
lowered before entering the boiler thoroughly condensing the vapour. Another way of
improving the efficiency of the turbine is through the reheating and reheat cycle. In the
Brayton cycle 2 turbines are used instead of 1. One of the turbines job is to drive the
compressor and the other turbine is there to generate net work output.

References:

 https://www.tau.ac.il/~tsirel/dump/Static/knowino.org/wiki/Compressibility_factor_(gases).
html last visited 14/05/20
 https://www.ecourses.ou.edu/cgi-bin/ebook.cgi?topic=th&chap_sec=06.5&page=theory last
 PHYSICAL REVIEW E 87, 042111 (2013) Adequacy of the virial equation of state and cluster
expansion, National University of Shipbuilding Geroyev Stalingrada avenue 9, Mykolayiv
54025, Ukraine (Received 8 December 2012; revised manuscript received 31 March 2013;
published 15 April 2013
 www.chemlibretexts.org , real gases (Deviations from ideal Behaviour), visited 16/05/2020
 https://www.mechanicaltutorial.com/rankine-cycle-efficiency
 Thermodynamics and Heat Power, Eighth Edition. By Irving Granet (Professor of engineering
city university of New York) and Maurice Bluestein (Professor Emertus, Indiana university-
Purdue University Indianapolis).