1

Material Balances

Material balances are necessary for the thermodynamic analysis of any process. The conservation principle states that the quantities of mass, energy and momentum cannot be created or destroyed. These quantities remain in balance in thermodynamic systems. First, we will look into detail in conservation of mass. In a closed system the mass is conserved (remains constant) by definition (The closed system is a system of fixed mass and there is no mass transfer across the system boundary). For an open system there is a flow across the boundary and mass can enter and leave the system. In this case the conservation of mass should also apply. If the mass flow rate entering an open system is exactly equal to the mass flow rate on leaving, and there is no change of mass flow rate with time, the flow is named as steady. So in the case of steady state flow if two mass streams m 1 and m 2 are entering into a system (as shown in Figure (3.1)) a mass stream m of equal magnitude, i.e. ( m + m )
1 2

should leave the system. mass flow rate in m +m 1 2 = mass flow rate out =m

(3.1)

Figure 3.1 : Material balance for a steady flow process. For unsteady flow processes (e.g., the filling of a gas cylinder) the conservation of mass is given as: mass entering the - mass leaving the = gain (or loss) of mass in the system system system So the conservation of mass may be written in most general form as under: dm( ) = me ( ) ma ( ) d

(3.2) m ( ) and m ( ) represent the mass streams at the entry and exit respectively, and where e a dm( ) d is the change in mass of the system with time. If there are more than one streams

entering and leaving the system then dm( ) = mi ( ) m j ( ) d i j

(3.3)

where the first summation is done over all the mass streams entering the system and the second summation over all the mass streams leaving the system. For steady flow processes, i.e. the processes for which the properties do not change with time at any point within the system equation (3.3) simplifies to m = m
i i j j

(3.4)

3.1

Thermal Conversions (Thermal Transformation of Matter)

All the changes which are brought about in the properties of matter without the occurrence of a chemical reaction are termed as thermal transformations. For example, the changes in temperature, pressure or composition of matter may be effected by thermal effects. In this case the amounts of individual components remain constant (in the absence of chemical reactions no new products will be formed).

3.1.1 Pure Substances

For processes where pure substances are used as working fluids, the material balance is simple. For steady flow processes the mass stream of pure substances entering the system must leave the system as such. A common application is in the water / steam cycle of a steam power plant. Figure 3.2 shows the schematic diagram of a simple steam power plant and Figure 3.3 shows the mass flow diagram of the water / steam cycle. Fresh steam produced in the boiler flows with a mass flow rate of m = 51 kg/s into the steam turbine. In the turbine it is divided into streams a) and b). The stream a ( m a= 11 kg/s) is directly fed to the condenser. The stream b ( m = 40 kg/s) is first used for external heating then passes to an economizer
b

(preheater) and finally to the condenser. The total stream ( m = 51 kg/s) is then fed back to the boiler. The magnitudes of the streams m , m a and m b are graphically shown in Fig. 3.3. A mass balance across the turbine shows that the steam stream of 51 kg/s entering the turbine is separated into two streams in m a (11 kg/s) and m b (40 kg/s). For such processes of nonreacting systems the balance of number of moles may also be done instead of mass balance.

Figure 3.2 : Schematic diagram of water/steam cycle of a steam power plant.

Figure 3.3 : Mass flow diagram of water/steam cycle.

3.1.2 Mixtures
The conservation of total mass is also valid for the processes where mixtures are used (for example, in the separation of petroleum oil in its various fractions). In the absence of any chemical reaction, the conservation of mass of individual components is valid. For example, if a mixture of water and alcohol is distilled for separation into pure water and pure alcohol, then the mass of water originally present in the mixture is found afterwards as pure water and the mass of alcohol in the mixture as pure alcohol. As no new products are formed through chemical reactions, the total number of moles and the number of moles of individual components remain constant during thermal transformation of matter. For the process where more than one stream is present, the material balance may be done easily for total amount and for the individual components. In general, we have as many material balances as the number of components in a process.

3.2

Chemical Conversions

A number of thermodynamic problems involve reacting systems i.e. where chemical reactions do take place. Among the most familiar of these are the combustion reactions of hydrocarbon fuels which are used in power plants. So it is necessary to consider the material balance for reacting systems. The conservation of mass also holds for the reacting systems, i.e. for systems where chemical reactions take place. However, here the conservation of the mass of individual components does not hold as some of the components (species) disappear as a result of chemical reactions and some new components (species) are formed during the reaction. The total number of moles and the number of moles of individual components are not preserved (do not remain constant). We will now look these conversions in detail.

3.2.1 Chemical Reactions, Stoichiometry

A chemical equation is a shorthand method for describing a chemical transformation. The substances on the left-hand side of the equation are called reactants and those on the right- hand side are called products. The equation H2O + CH4 H2 + CO (3.5)

expresses the fact that water reacts with methane to form hydrogen and carbon monoxide. If the equation is balanced, H2O + CH4 3 H2 + CO (3.6)

it expresses the fact that the number of atoms of a given kind must be the same on both sides of equation. A balanced chemical equation is an expression of the law of conservation of

mass. Chemical equations provide the relationship between the masses of various reactants and products, which is of much importance for the thermodynamic analysis of reacting systems. The equation (3.6) states that 1 mol of water will react with 1 mol of methane to form 3 mols of hydrogen and 1 mol of carbon monoxide. One sees that the number of moles M change. If we put the molecular masses (molecular weights) of the components ( H 2O = M CH 4 M H2 18.015 g/mol; = 16.043 g/mol; = 2.0158 g/mol and MCO = 28.011 g/mol) in equation (3.6) we get 18.015g H2O + 16.043g CH4 6.047g H2 + 28.011g CO (3.7)

Equation (3.7) states that 18.015g of water will react with 16.043g of methane completely to form 3 2.0158 = 6.047g of hydrogen and 28.011g of carbon monoxide. We see from equation (3.7) that the total mass (i.e., 34.058) is preserved (remains constant) in chemical reactions. We also see from the balanced equation (3.6) that the elements are conserved in reacting systems (here, 6 hydrogen atoms, 1 carbon atom, and 1 oxygen atom). The combustion reactions, e.g. CH 4 ( g ) + 2O2 ( g ) CO2 ( g ) + 2 H 2O ( g ) and C3 H 8 ( g ) + 5O2 ( g ) 3CO2 ( g ) + 4 H 2O ( g )

take place in only one direction, that means if we start with 1 mol of CH4 and 2 mol O2 (stoichiometric amounts) then on completion of reaction we will get only the products CO 2 (1 mol) and H2O (2 mol).

3.2.2 The Degree of Reaction

It is convenient to write the chemical reaction in a more general form |v1|A1(p) + |v2|A2(p) +.... |v3|A3(p) + |v4|A4(p) (3.8)

where Aj(p) represent the chemical formula for component (species) j and includes a designation (p) of the physical state of j, e.g. (s) for solid, (l) for liquid or (g) for gas. The |vj| are stoichiometric coefficients. The vj themselves are called stoichiometric numbers. By convention, vj is negative for a reactant and positive for a product. If an inert component is present (i.e., if a component does not participate in reaction), its stoichiometric number is zero. Thus for the reaction (3.6) the stoichiometric numbers are: v H 2O = -1 ; v CH 4 = -1 ; v H 2 = +3 ; vCO = +1

In a closed system undergoing chemical reaction, the changes in the numbers of moles of the components present are not independent of one another. The changes in the numbers of moles of components are directly proportional to the stoichiometric numbers. Thus for

reaction (3.6) if 0.5 mol of water is consumed (disappears), 0.5 mol of CH 4 must also be consumed and 1.5 mol of H2 and 0.5 mol of CO will be formed. Thus dn1 dn 2 dn3 = = = ... = d v1 v2 v3

(3.9)

where dn1, dn2 etc. are the changes in the number of moles of a component, d is a quantity which represents the amount of reaction. Equation (3.9) may be written in a general from dnj = vjd (3.10)

This new variable characterizes the degree to which a reaction has proceeded and is called the degree of reaction (or extent of reaction or reaction coordinate). Equation (3.10) gives the changes in with respect to the changes in the numbers of moles of the components taking part in the reaction. itself is specified by the value zero in the initial state (unreacted state) i.e. when nj is nj(o). The integration of equation (3.10) from an initial state when = 0 and nj = nj(o) to any state after the reaction has proceeded up to an arbitrary amount gives
nj

n (j 0 )

dn

= v j d
0

or

nj = nj(o) + vj

(3.11)

Equation (3.11) describes a relation between the number of moles of any component present after a given time to the number of moles present before the reaction has started. The reaction coordinate specifies the extent to which reaction has proceeded. The value of depends on the overall reaction equation and on the initial amount of the components. The maximum value of max will indicate that at least one of the reactants of given reaction is totally consumed. For example, if we start with 1 mol methane and 2 mol oxygen then for the reaction, CH4(g) + 2 O2(g) CO2(g)+ 2 H2O(g) which runs completely to the right side n CH 4 = 1 1 That means if = 1 then all the methane is consumed. The maximum extent (degree) of such a reaction , max, may be calculated directly from a knowledge of reaction equation and the initial amounts of the reactants. Summation of equation (3.11) over all the components gives (3.12)

n = n(o) + v where n = nj ; n(o) = nj(o) und v = vj. Thus the mole fraction xj of the components present are related to xj = nj n = n (j0 ) + v j n ( 0 ) + v

(3.13)

(3.14)

Hence the mole fractions of the components in a reacting system of a single reaction are functions of the single variable .

3.2.3 Degree of Conversion and Yield

The extent (degree) of a reaction, which does not proceed to the end (i.e. the reactants are not completely converted into products) cannot be determined alone from the knowledge of reaction equation and the initial amounts of the reactants. The synthesis of ammonia is an example of such reactions. The reaction N2(g) + 3H2(g) 2NH3(g) (3.15)

does not proceed to the right side completely (i.e. up to the end). For the ammonia synthesis in a stationary flow process it will mean that nitrogen and hydrogen also exist together with ammonia in the product stream. To calculate the for such reactions, we need additional information. For example, if besides the reaction equation and the data of the reactant streams the amount of one of the components in the product stream is known, the can be calculated with the help of equation (3.11). If the amount (mole fraction) of one of the components in the product stream is known the amounts of all other components are fixed. The terms degree of conversion and yield are used to characterize such incomplete chemical transformations. The degree of conversion, Ui, is defined in terms of the extent of the consumption of a component in a reaction ni( 0 ) ni (0) U = ni
i

(3.16)

It is the ratio of the amount of a component i consumed during the reaction to its initial amount. For reactions which start with the stoichiometric composition and proceed up to the end, the degree of conversion for every reactant is 1. For example, if we start the reaction (3.15) with 1 mol of N2 and 3 mol of H2 (stoichiometric composition of the reactants) and the reaction proceeds up to the end then U N 2 = U H 2 = 1. The yield of a component i with reference to one of the reactants k is the ratio of the amount of the component i formed and the initial amount of the reactant k.

Ai,k=

ni ni( 0 ) ( nk0 )

(3.17)

( 0) n NH 3 n NH 3

( 0) n NH 3 n NH 3

For example, A NH 3 , N 2 =

( n N02)

and

A NH 3 , H 2 =

( n H02)

3.2.4 Equilibrium Constant

Another important term used for the description of chemical equilibrium is the equilibrium constant. The equilibrium constant determines the direction and the extent of change (maximum possible yield) for any given set of conditions (temperature and pressure). A knowledge of equilibrium constants is essential for the production of useful substance from raw materials. For the above reaction (ammonia synthesis), if the ideal gas mixture model is used, the equilibrium constant is defined as ( K (T ) = ( x NH 3 p p0 )2 =(
2 x NH 3

xN2 p xH2 p 3 )( 0 ) p0 p

xN2 x

3 H2

)(

p 2 ) p0 (3.18)

or in general for any reaction in gaseous form where the ideal gas mixture model may be used K (T ) = i( xi p vi p ) = i( xi ) vi ( 0 ) 0 p p
v

(3.19)

where p0 = 1 bar and v = vi, the algebraic sum of the stoichiometric numbers of the reaction equation. The equilibrium constant depends strongly on temperature. A small value of K will indicate that at equilibrium the concentrations of products are very small and a large part of reactants is not consumed ( remains unreacted ), i.e. the reaction does not proceed to the right hand side to an appreciable extent. The pressure dependence of the equilibrium concentrations is given by the term p v ( 0) p . If v = 0 i.e. the sum of stoichiometric numbers of reactants and the products are equal then the equilibrium is independent of pressure. Similarly, for the reaction of liquid mixtures and if the model of ideal solutions is applicable, the equilibrium constant is given as K (T ) = i( xi ) vi The pressure dependence may be neglected for liquid mixtures. (3.20)

3.2.5 Balance of the Elements

The matter conversion through chemical reactions may be described easily if the overall reaction equation is known. However, sometimes the composition of the products and the initial reactants amounts is known, but the overall reaction equation which describes the conversion is not known. In such cases we take the help of conservation of elements. The number of individual elements in the products should be the same as in the reactants. In such cases if the number of elements is equal to the number of unknown amounts (mole fraction) of the products, the composition of the product mixture may be calculated easily. It will be shown in Example 3.1.

3.2.6 Material Balance in a Process

The material balances for the analysis of chemical or thermochemical processes may sometimes be quite complicated. Hence special care should be taken in selecting the control volume area for the different mass balances. It should be tried that every mass balance area contains only one unknown substance amount, which can then be calculated. The following example will explain this.

Example 3.1: Iron oxide is reduced in a blast furnace. The surplus amounts of carbon, hydrogen, water and air lead to the formation of blast furnace gas (throat gas). The quantities of the reactants are mC = 361.15 kg m H2 m O2 m N2 = 7.56 kg = 704.68 kg = 985.60 kg m H 2O = 10 kg

Calculate the composition of the blast furnace gas. It may be assumed that the blast furnace gas is made up of CO, CO2, H2 and N2 only. N2 is to be treated as an inert substance. Solution: The reaction equation may be written as 361.15 kg C + 7.56 kg H2 + 10 kg H2O + 704.68 kg O2 + 985.60 kg N2 a kg CO + b kg CO2 + c kg H2 + d kg N2 The equation may be simplified by changing the masses of substances into moles using the molecular weights: [MC = 12.011; M H = 2.016; M H 2O = 18.015; M O2 = 31.999; M N 2 = 28.013 MCO = 28.011; M
2

CO2

= 44.011]

30.07 kmol C + 3.75 kmol H2 + 0.56 kmol H2O+ 22.02 kmol O2 + 35.18 kmol N2 x CO + y CO2 + z H2 + w N2 As the nitrogen does not take part in chemical reaction its amount on the both sides of the equation may be equated. It follows then w =35.18 kmol We now calculate unknown amounts (moles) of CO, CO2 and H2 from the balance of elements. In this example we have three elements and so the three unknown amounts of CO, CO2 and H2 may be calculated. We count the number of moles of CO, CO2 and H2 on both sides of equation and equate them. C: O2: H2: 30.07 kmol = x + y 1 1 22.02 kmol + 2 0.56 kmol= 2 x + y (0.56 + 3.75)kmol = z (a) (b) (c)

From (c) we get z = 4.31 kmol. Subtracting eq. (b) from (a) we get 1 2 x = 7.77 kmol or x = 15.54 kmol. Putting the value of x in equation (a) we get y = 14.53 kmol. So we get the amounts of individual products. Now the total amount of products nbfg = 15.54 kmol +14.53 kmol + 4.31 kmol + 35.18 kmol = 69.56 kmol. And the composition 15.54 x CO = 69.56 = 0.2234 14.53 x CO2 = 69.56 = 0.2089 4.31 x H = 69.56 = 0.0619 35.18 x N 2 = 69.56 = 0.5058.
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