APPLIED THERMODYNAMICS TDA-301T 2012

Lecture 7: Tutorial Chapters 2 - 4,

By

Prof Alex Sofianos

Bsc Chem Eng, Msc, PhD Ind Chem (Germany), MBL (UNISA)

Course Contents
1. 2. 3. 4. 5. 6. 7. 8. 9. Introduction Conservation of Mass Conservation of Energy Entropy An additional Balance Equation Liquefaction, Power Cycles, Explosions Thermodynamic Properties of Real Substances Equilibrium and Stability One Component Thermodynamics of Multi-Component Systems Estimation of Gibbs Energy and Fugacity of a Component in a Mixture 10. Vapor-Liquid Equilibrium in Mixtures 11. Chemical Equilibrium
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Course Books
1. Chemical, Biochemical & Engineering Thermodynamics 4 Edition, Stanley I. Sandler , John Wiley and Sons (2006) 2. Introduction to Chemical Engineering Thermodynamics (The McGraw-Hill Series in Civil and Environmental Engineering) by J.M. Smith, Hendrik C. Van Ness, and Michael Abbott (2004) 3. Introduction to Chemical Engineering Thermodynamics by J.M. Smith (2001) 4. Engineering and Chemical Thermodynamics by Milo D. Koretsky (2003)
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Objectives
At the end of this Chapter, the student must: Be able to solve problems involving the liquefaction of gases Be able to compute the work that can be obtained from different types of power cycles and using different working fluids Be able to compute the work required for the operation of refrigeration cycles Be able to compute the energy release resulting from the uncontrolled explosion of a gas
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Mass Balance
ILLUSTRATION 2.2-3
Use of the Rate-of-Change Form of the Mass Balance Gas is being removed from a high-pressure storage tank through a device that removes 1 percent of the current contents of the tank each minute. If the tank initially contains 1000 mols of gas, how much will remain at the end of 20 minutes? SOLUTION Since 1 percent of the gas is removed at any time, the rate at which gas leaves the tank will change with time.
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Mass Balance
ILLUSTRATION 2.2-3
Initially gas is leaving at the rate of 0.01 1000 mol/min = 10 mol/min. Later when only 900 mol of gas remain in the tank, the exiting flow rate will be 0.01900 mol/min = 9 mol/min. The exiting flow rate is continuously changing with time! Use the rate-of-change or differential form of the mass (mole) balance:

Mass Balance
ILLUSTRATION 2.2-3
Rate-of-change form of the mass balance (Eq. 2.2-1b) around the tank, that has only a single flow term

If we solve this first-order differential equation:

Then we obtain: N(t=20) = N(t=0) e -0.01t Or N(t=20) = 1000 e -0.01x20 = 1000 e -0.2 = 818.7 mol
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Mass Balance
ILLUSTRATION 2.2-3
Rate-of-change form of the mass balance (Eq. 2.2-1b) around the tank, that has only a single flow term

If we solve this first-order differential equation:

Then we obtain: N(t=20) = N(t=0) e -0.01t Or N(t=20) = 1000 e -0.01x20 = 1000 e -0.2 = 818.7 mol
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Mass Balance
CONCLUSION 2.2-3
To solve any problem in which the mass (or molar) flow rate changes with time, we need to use the differential or rate-of-change form of the mass balance. For problems in which all of the flow terms are constant, we can use the general difference form of the mass balance (which has been obtained from the rate-ofchange form by integration over time), or we can use the rate-of-change form and then integrate over time. However, it is important to emphasize that if one (or more) flow rates are changing with time, the rate-ofchange form must be used.
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Mass Balance
ILLUSTRATION 2.2-4
Use of the Rate-of-Change Form of the Mass Balance An open cylindrical tank with a base area of 1 m2 and a height of 10 m contains 5 m3 of water. As a result of corrosion, the tank develops a leak at its bottom. The rate at which water leaves the tank through the leak is

where P is the pressure difference in bar between the fluid at the base of the tank and the atmosphere. Determine the amount of water in the tank at any time.
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Mass Balance
ILLUSTRATION 2.2-4
SOLUTION Pressure at the bottom of the tank is equal to the atmosphere pressure plus the hydrostatic pressure due to the water above the leak!
P = 1.013 bar + g h

where is the density of water and h is the height of water above the leak; g is the acceleration due to gravity; Therefore, P = (1.013 + gh) 1.013 = g h Then:

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Mass Balance
ILLUSTRATION 2.2-4
Since the height of fluid in the tank is changing with time, the flow rate of the leak will change with time. Therefore, to solve the problem, we must use the rateof-change form of the mass balance. First we calculate the mass of water in the tank at a time t: The mass balance on the contents of the tank at any time may be expressed as:

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Mass Balance
ILLUSTRATION 2.2-4
The negative sign arises because the flow is out of the tank!

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() = -0.1566 h(t) or d h(t) = -0.1566 10-3 h(t) dt

Integrating this equation between t = 0 and any later time t yields:

or

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Mass Balance
CONCLUSION 2.2-4
Since the rate of flow of water out of the tank depends on the hydrostatic pressure due to the water column above the leak, and since the height of this column changes with time, again we must use the rate-of-change form of the mass balance to solve the problem. It is important in any problem to be able to recognize whether the flows are steady, in which case the difference form of the mass balance can be used, or the flows vary with time, as is the case here, in which case the rate-of-change form of the mass balance must be used.
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Mass Balance
CONCLUSION 2.2-4
Since the rate of flow of water out of the tank depends on the hydrostatic pressure due to the water column above the leak, and since the height of this column changes with time, again we must use the rate-of-change form of the mass balance to solve the problem. It is important in any problem to be able to recognize whether the flows are steady, in which case the difference form of the mass balance can be used, or the flows vary with time, as is the case here, in which case the rate-of-change form of the mass balance must be used.
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Multicomponent System
With Chemical Reaction
When chemical reactions occur, the mass (or mole) balance for each species is more complicated since the amount of the species can increase or decrease as a result of the reactions. Here we will consider mass balances when there is only a single chemical reaction; we will write the mass balances using number of moles only, since the stoichiometry of chemical reactions is usually written in terms of the number of moles of each species that undergoes chemical reaction rather than the mass of each species that reacts
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Multicomponent System
With Chemical Reaction
Using the notation (i)k for the rate at which moles of species i enter (if positive) or leave (if negative) in flow stream k, we have the differential or rate-of-change form of the mass balance on species i

Rate-of-change mass balance with chemical reaction on a molar basis

last term is new and describes the rate at which species i is produced or consumed within the system by chemical reaction
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Multicomponent System
With Chemical Reaction
The difference form of this equation, obtained by integrating over the time period from t1 to t2, is

Difference form of the mass balance with chemical reaction on a molar basis

Summation terms after the equal signs are the changes in the number of moles of the species due to the flow streams, and the second terms are the result of the chemical reaction 19

Multicomponent System
With Chemical Reaction
If the flow rate of a stream is steady (i.e, (i)k is constant), then:

Difference form of the mass balance with steady flow rate

EXAMPLE Mass (mole) balance for a reactor in which the following chemical reaction occurs:

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Multicomponent System
With Chemical Reaction
During the reaction neither ethylene nor chlorine is completely consumed. Stream 1 is pure ethylene and stream 2 is pure chlorine; exit streams [i.e., (...)3] are negative in value. The mass balances for these species, are as follows:

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Multicomponent System
With Chemical Reaction
From the stoichiometry of this reaction, all the reaction rate terms are interrelated. The rate at which ethylene chloride is created, that is, the number of moles per second, is equal to the rate at which ethylene is consumed, which is also equal to the rate at which chlorine is consumed! In other words:

Equation above can then be simplified:

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Multicomponent System
With Chemical Reaction
General chemical reaction equation:

With the molar stoichiometric coefficients can be re-written as:

or as:

with i is the stoichiometric coefficient of species i,

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Multicomponent System
With Chemical Reaction
We will use Ni to represent the number of moles of species i in the system at any time t and Ni,0 to be the initial number of moles of species i. However, Ni and Ni,0 are related through the reaction variable X, called the molar extent of reaction, and the stoichiometric coefficients i by the equation:

or : with i is the stoichiometric coefficient of species i

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Example:
ILLUSTRATION 2.3.-1
The electrolytic decomposition of water to form hydrogen and oxygen occurs as follows: Initially, only 3.0 mol of water are present in a closed system. At some later time it is found that 1.2 mol of H2 and 1.8 mol of H2O are present. a. Show that the molar extents of reaction based on H2 and H2O are equal. b. Compute the number of moles of O2 in the system. SOLUTION a. Reaction is written as
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Example:
ILLUSTRATION 2.3.-1
So that:

b.- Using equation Ni = Ni,0 + i X we have:

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Example:
ILLUSTRATION 2.3.-1
The rate of change of the number of the moles of species i resulting from a chemical reaction is:

where the subscript rxn indicates that this is the rate of change of the number of moles of species i due to chemical reaction alone, and is the rate of change of the molar extent of reaction.

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Rate-of-change Form of the Mass Balance

The balance equation for species i is therefore:

Rate-of-change form of the mass balance with chemical reaction: molar basis

And the here the subscript rxn indicates that this is the rate of change of the number of moles of species i due to chemical reaction alone, and is the rate of change of the molar extent of reaction.
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 We can now write the mass balances for the ethylene dichloride synthesis using the molar extent of the reaction:

Mass Balance with Extent of Reaction

As:

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Performing material balances on reactive systems is slightly more complex than for non-reactive systems. For simplicity, we will only focus on reactive processes that are open systems which are run at steady state. N2 + 3H2 -> 2NH3

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N2 + 3H2 -> 2NH3

This yields a simplified balance equation of: i i0 + G C = 0 or i0 = i + G C G - Generation C - Consumption ; both through chemical reaction

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N2 + 3H2 -> 2NH3

This yields a simplified balance equation of: i i0 + G C = 0 or i0 = i + G C we will switch to using molar quantities that we get: i0 = i + G C
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N2 + 3H2 -> 2NH3

The extent of reaction (X) is a method of quantifying how many "times" a reaction has occurred. It has units of moles/time and numerically, it is chosen such that the stoichiometric coefficient times X is equal to the quantity of species reacted.

2O= 8 kmol/h = N2I + GN2 CN2= 10 kmol/h + 0 1X

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N2 + 3H2 -> 2NH3

N2O= 8 kmol/h = N2I + GN2 CN2= 10 kmol/h + 0 1X OUT IN Similarly: H2O= 15 kmol/h = H2I + GH2 CH2= H2I + 0 3X NH3O= 4 kmol/h = NH3I + GNH3 CNH3= 0 + 2X 0
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Extent of Reaction X
Typically "reactants" have g=0, while "products" have a zero initial concentration and have c=0. This obviously becomes more complex when multiple reactions take place. Using the extent of reaction method for systems with multiple reactions involves including a new value of X for each reaction, and then calculating c and g as the sum of applicable X 's. EXAMPLE Reactions: A B 2B C
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Extent of Reaction X
EXAMPLE Reactions:

A B 2B C

If we assign X1 to the first reaction and X2 to the second, we get expressions that look like: AO = AI + G A CA = AI + 0 1X1 BO = BI + G B CB = BI + 1X1 2X2 CO = CI + G C CC = CI + 1 X2 0
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Problem 2.4
The following reaction occurs in air: At 20 0C the rate of this reaction is given by the formula:

for t in seconds and concentrations in kmol/m3. The reaction occurs in a constant-volume, 2-L vessel, and the initial concentration of NO is 1 kmol/m3 and that of O2 is 3 kmol/m3 a. If 0.5 mol of NO reacts, how much NO2 is produced? b. Determine how long it would take for 0.5 mol of NO to have reacted. 37

Problem 2.4
The following reaction occurs in air: a. If 0.5 mol of NO reacts, how much NO2 is produced?

Equation may be re-written as: 2NO2 2NO O2 = 0 By division with 2 we obtain: NO2 1 O 2 2

NO = 0

From the equation we can see at once that 1 mol NO would be consumed in order to produce 1 mol NO2 ; therefore, 0.5 mol NO would produce 0.5 mol NO2

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Problem 2.4
b.- We set up a stoichiometric matrix as follows: Determine the initial concentrations of the reactants: Reactants NO O2 NO2 Stoich. Initial Concentration Coefficients Concentration at X -2 1 12X - 1 3 3X 2 0 2X

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Problem 2.4
b.- We determine the actual mol numbers from the concentrations: For NO we have: CNO = 1 kmol/m3 We know that therefore: and
CNO = ;

NNO = V CNO NNO = 2 L x 1 mol/L = 2 mol

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ILLUSTRATION 2.3-2
Mass Balance for a Mixture with Chemical Reaction At high temperatures acetaldehyde (CH3CHO) dissociates into methane and carbon monoxide by the following reaction: At 520 oC the rate at which acetaldehyde dissociates is given by the formula:

C is the concentration in kmol/m3 The reaction occurs in a constant-volume, 1-L vessel, and the initial concentration of acetaldehyde is 10 kmol/m3. 41

ILLUSTRATION 2.3-2
a. If 5 mols of the acetaldehyde reacts, how much methane and carbon monoxide is produced? b. Develop expressions for the amounts of acetaldehyde, methane, and carbon monoxide present at any time, and determine how long it would take for 5 mol of acetaldehyde to have reacted. SOLUTION First determine the initial amount of acetaldehyde present.
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ILLUSTRATION 2.3-2
Since the initial concentration is:

we conclude that:

Then we write the stoichiometry for the reaction

in terms of the molar extent of reaction X as follows:

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ILLUSTRATION 2.3-2
To determine the amounts of each species after a given amount of acetaldehyde has reacted, we can use the difference form of the mass balance for this system with no flows of species into or out of the reactor:

we get for acetaldehyde: or X = 5 mol. Then amounts of the other species are: NCH4 (t) = X = 5 mol and NCO(t) = X = 5 mol
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ILLUSTRATION 2.3-2
b.-To determine the amount of each species as a function of time is more difficult and must be done using the rateof-change form of the mass balance since the rate of reaction and therefore the value of X change with time. We can use the mass balance for one of the species to determine the time variation of X, and then can use the expression for X(t) to obtain the compositions of all species in the reaction as a function of time. Since the rate expression is written for acetaldehyde, we will use this substance to determine the time dependence of X
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ILLUSTRATION 2.3-2
There are no flows into or out of the reactor, therefore:

can be written for acetaldehyde:

Next the reaction rate expression can be written as

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ILLUSTRATION 2.3-2
The latter , after using N CH3CHO = 10 X can become:

Next, integrating from t = 0, at which X = 0, to some other time t gives: or extent of the reaction as a function of time! Example: solving this equation for X(t) = 5 mol gives t = 0.208 s; that is, half of the acetaldehyde has decomposed within 0.2 seconds
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ILLUSTRATION 2.3-3
Mass Balance for a Liquid Mixture with a Reversible Reaction

The ester ethyl acetate is produced by the reversible reaction Reaction activated by a sulfuric acid catalyst . The rate of ethyl acetate production has been found, from the analysis of chemical kinetics data, to be given by the following equation:
subscripts EA, A, E, and W denote ethyl acetate, acetic acid, ethanol, and water, respectively C is the concentration of each species in units of kmol/m3
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ILLUSTRATION 2.3-3
The values of the reaction rate constants at 100C and the catalyst concentration of interest are:
k = 4.76 104 m3/kmol min k = 1.63 104 m3/kmol min

Develop expressions for the number of moles of each species as a function of time if the feed to the reactor is 1 m3 of an aqueous solution that initially contains 250 kg of acetic acid (A) and 500 kg of ethanol (E). The density of the solution may be assumed to be constant and equal to 1040 kg/m3
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ILLUSTRATION 2.3-3
The reactor will be operated at a sufficiently high pressure that negligible amounts of reactants or products vaporize. Compute the number of moles of each species present at a time t (t=100 minutes) after the reaction has started, and at infinite time when the reaction will have stopped and the system is at equilibrium.

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ILLUSTRATION 2.3-3
SOLUTION The reaction rate expression is a function of the compositions, which are changing as a function of time, the mass balance for each species must be written in the rate-of-change form. Since the species mole numbers and concentrations are functions of the molar extent of reaction, X, we first determine how X varies with time by solving the mass balance for one species. Since the reaction rate is given for ethyl acetate we have to use that species! Once the amount of ethyl acetate is known, we can compute the other species! 51

ILLUSTRATION 2.3-3
The initial concentration of each species, expressed as kmol/m3 is:

Since there is only 1 m3 the initial amount of each species is:

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ILLUSTRATION 2.3-3
If we consider the reaction stoichiometry, the amount of each species present at any time (in kmol) and its concentration (since 1 m3 of volume is being considered) is

And NEA = X CEA = X The concentration of a species is equal to the number of moles N divided by the volume V, i.e. C=

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ILLUSTRATION 2.3-3
the chemical reaction rate equation can be written as

By using V = 1 m3 and the mole numbers, we can simplify:

or
and
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ILLUSTRATION 2.3-3
This can be re-arranged to:

And integrated between t= 0 and t = t; this yields:

or And after solving for X X in kmol t in minutes

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ILLUSTRATION 2.3-3
This leads to:

and At 100 minutes, X = 1.40 kmol so that: NA = 4.17 X = 4.17 1.4 = 2.77 NE = 9.5, NW = 17.5 NEA = 1.4
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ILLUSTRATION 2.3-3
From

At t = infinite, i.e., at equilibrium: X = 2.3911 kmol so that: NA = 4.17 X = 4.17 2.39 = 1.78 NE = 8.51 NW = 18.49 NEA = 2.39

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THANK YOU

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