1 ‫موازنة املادة يف املفاعالت الكيميائية‬

2 Material Balance on Chemical Reactors

3 Four Lectures (2 Hours /Week)
4 Dr. AMJED AHMED
5 Ref: Richard M. Felder. Elementary Principles of Chemical Processes, 3rd edition 2005.
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7 • Stoichiometric equation is a statement of the relative number of molecules that participate
8 in the chemical reaction. The number of atoms of each atomic species must be the same on
9 both sides of the equation.
10 • Stoichiometric ratio is obtained from the balanced reaction equation for two reactants.
11 2 SO2 + O2 → 2 SO3
12 Stoichiometric ratio is 2 moles of SO2 for every mole of O2.
13 • Limiting Reactant ‫ المادة المحددة‬is a reactant that would run out ‫ينفذ‬, and the other reactants
14 are excess reactants .‫ المواد الفائضة‬Thus,
𝑛̇ 𝐴𝑜 − 𝑛𝐴,𝑠𝑡𝑜𝑖𝑐ℎ
15 Fractional excess of the reactant = (4.6 − 1)
𝑛𝐴,𝑠𝑡𝑜𝑖𝑐ℎ
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17 If 160 mol of SO2 reacted with 100 mol of O2, the SO2 would run out first ‫ينفذ اوال‬.
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19 • Fractional Conversion of the reactant (f or x) is: ‫نسبة التحول‬
𝑀𝑜𝑙𝑒𝑠 𝑅𝑒𝑎𝑐𝑡𝑒𝑑 𝑛̇ 𝐴𝑜 − 𝑛̇ 𝐴
20 𝑥= = (4.6 − 2)
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐹𝑒𝑒𝑑 𝑛̇ 𝐴𝑜
21 𝑛̇ 𝐴 = 𝑛̇ 𝐴𝑜 (1 − 𝑥)
22
23 • Extent of Reaction (ξ) molar flow rate of specie A in the final state is,
24 𝑛̇ 𝐴 = 𝑛̇ 𝐴𝑜 + 𝜉𝑣𝐴 (4.6 − 3)
𝑛̇ 𝐴𝑜 − 𝑛̇ 𝐴
25 𝜉̇ = (9.1 − 3)
|𝑣𝐴 |
26 ṅA is unreacted molar flow rate, ‫موالت المادة الغير متفاعلة‬
27 ṅAo is molar flow rate in the feed,
28 vA is stoichiometric coefficient, making it negative for reactants and positive for products.
29 vSO3 = 2 vSO2 = 2 vO2 = 1
 Material Balance on the Chemical Reactors 2

1 Example: Fed to a reactor is 20 kmol of acetylene and 50 kmol of hydrogen to form ethane:
2 C2H2 + 2H2 → C2H6
3 The ratio of H2 to C2H2 in the feed is (50/20 = 2.5). Hydrogen is fed in a greater-than-
4 stoichiometric proportion to acetylene (2/1 = 2). Acetylene is therefore the limiting reactant.
5 From Equation 4.6-1,
50 − 40
6 Fractional excess of H2 = = 0.25
40
7 We say that there is 25% excess hydrogen in the feed.
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9 Example: The feed to a continuous reactor consists of 100 mol/s of nitrogen, 300 mol/s of
10 hydrogen, and 1 mol/s of argon (inert gas). a fractional hydrogen conversion of 0.6.
11 N2 + 3H2 → 2 NH3
12 Calculate the product of hydrogen, and nitrogen and ammonia.
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18 H.W.: The oxidation of ethylene to produce ethylene oxide proceeds according to the equation.
19 The feed to a reactor contains 100 kmol C2H4 and 100 kmol O2

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21 1. Which reactant is limiting?
22 2. What is the percentage excess of the other reactant?
23 3. If the reaction proceeds to completion, how much of the excess reactant will be left;
24 how much C2H4O will be formed; and what is the extent of reaction?
25 4. If the reaction proceeds to a point where the f of the limiting reactant is 50%, how much
26 of each reactant and product is present at the end, and what is the extent of reaction?
27 5. If the reaction proceeds to a point where 60 kmol of O2 is left, what is the f of C2H4?
28 The f of O2? The extent of reaction?

Dr. Amjed Ahmed

 Material Balance on the Chemical Reactors 3

1 Example 4.6-1: Acrylonitrile is produced in the reaction of 10 mole% propylene, 12%

2 ammonia, and 78% air:
3 A fractional conversion of limiting reactant is 30%. Determine which reactant is limiting, the
4 percentage by which each of the other reactants is in excess, and the molar amounts of all
5 product gas.
6

7 Solution Taking 100 mol of feed as a basis

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13 Propylene is the limiting reactant. To determine the percentages by which ammonia and oxygen
14 are in excess, we must first determine the stoichiometric amounts of these reactants
15 corresponding to the amount of propylene in the feed (10 mol) and then apply Equation 4.6-1.

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18 However, from Equation 4.6-3,
19 nC3H6 = 10.0 mol C3H6 – ξ.  ξ = 3.0 mol
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21 from equation 4.6-3,

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 Material Balance on the Chemical Reactors 4

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2 Solution

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5 ‫) ر‬kg( ‫( اىل‬mol) ‫ ولتحول‬.M.wt ‫( بالقسمة عىل‬mol) ‫) فأننا نحولها اىل‬kg( ‫اذا الناتج مطلوب بوحدات‬
M.wt ‫نضب‬
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Dr. Amjed Ahmed

 Material Balance on the Chemical Reactors 5

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3 Solution
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 Material Balance on the Chemical Reactors 6

1 4.6c Equilibrium Compositions of Reversible Reactions

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3 Example 4.6-2: if the water gas shift reaction,

4 CO (g) + H2O (g)  CO (g) + H2 (g)

5 K is the reaction equilibrium constant as a function of the mole fractions which equal to 1 at
6 1105 K. The feed to a reactor contains 1 mol of CO, 2 mol of H2O, and no CO2 or H2, and the
7 reaction mixture comes to equilibrium at 1105 K. Calculate the equilibrium composition and
8 the fractional conversion of the limiting reactant.
9 Solution

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 Material Balance on the Chemical Reactors 7

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3 Solution

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 Material Balance on the Chemical Reactors 8

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 Material Balance on the Chemical Reactors 9

1 4.6d Yield, and Selectivity of Multiple Reactions ‫احلصيلة واالنتقائية للتفاعالت املتعددة‬
2 Reactants can usually combine in more than one way, and the product once formed may react
3 to yield something less desirable. The result of these side reactions is an economic loss: less of
4 the desired product is obtained for a given quantity of raw materials.
5 .‫التفاعالت الجانبية تستهلك المنتج المطلوب او المواد االصلية المتفاعلة‬
6 Example, ethylene can be produced by the dehydrogenation of ethane:
7 C2H6 → C2H4 + H2
8 Once some hydrogen is produced, it can react with ethane to produce methane:
9 C2H6 + H2 → 2CH4
10 Moreover, ethylene can react with ethane to produce propylene and methane:
11 C2H4 + C2H6 → C3H6 + CH4
12 Only the first reaction may be regarded as desirable; the second one consumes the reactant
13 without and the third consumes both the reactant and the desired product.
14 The terms Yield and Selectivity are used to describe the degree to which a desired reaction
15 predominates ‫ يهيمن على‬over competing side reactions. High values of the Yield and Selectivity
16 signify that the undesired side reactions have been successfully suppressed relative to the
17 desired reaction. .‫القيم العالية للحصيلة واالنتقائية تدل على ان نسبة المواد المطلوبة اعلى من المواد الغير المطلوبة‬

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19 Yield is as moles of desired product divided by either moles of reactant fed or moles of reactant
20 consumed in the reactor.
21 In a single reaction ṅA = ṅAo + νA ξ 4.6-3
22 In multiple reactions ṅA = ṅAo + ∑ νA,j ξ,j 4.6-6
23 Example: A pair of reactions in which ethylene is oxidized either
24 to ethylene oxide (desired) or to carbon dioxide (undesired):
25 Solution: The moles of the five species are,

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 Material Balance on the Chemical Reactors 10

1 Example 4.6-3: Take place in a continuous reactor at steady state in the reactions

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3 The feed contains 85 mole% ethane (C2H6) and the balance inert (I). The fractional conversion
4 of ethane is 0.501, and the fractional yield of ethylene (C2H4) is 0.471. Calculate the molar
5 composition of the product gas and the selectivity of ethylene to methane production.
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7 Solution: basis 100 mol feed
8 From Equation 4.6-6, the outlet component
9 amounts in terms of extents of reaction are:

10
𝑛2 (𝐶2𝐻4)
11 𝑬𝒕𝒉𝒚𝒍𝒆𝒏𝒆 𝒀𝒊𝒆𝒍𝒅 = 0.471 =
𝑀𝑎𝑥. 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑

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14 Ethane Conversion
15 If the fractional conversion of ethane is 0.501, the fraction unconverted must be (1 – 0.501).

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 Material Balance on the Chemical Reactors 11

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 Material Balance on the Chemical Reactors 12

1 4.7 BALANCES ON REACTIVE PROCESSES

2 In general, systems that involve chemical reactions may be analyzed using
3 (a) Molecular species balances (the approach always used for nonreactive systems),
4 (b) Atomic species balances,
5 (c) Extents of reaction.
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7 (a) Molecular Balance: (the approach always used for nonreactive systems), The balance
8 equation for a steady-state process is
9 Input + Generation = Output + Consumption.
10 The degree-of-freedom analysis is as follows:
11 + No. unknown variables
12 + No. independent chemical reactions
13 – No. independent molecular species balances
14 – No. other equations relating unknown variables
15 Degrees of freedom
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17 Example: A dehydrogenation of ethane is

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 Material Balance on the Chemical Reactors 13

1 (b) Atomic Balance: atoms can neither be created (generation = 0) nor destroyed
2 (consumption = 0) in a chemical reaction. Balance equation can be written
3 Input = Output
4 Each approach leads to the same results, but any one of them
5 The degree-of-freedom analysis is as follows:
6 No. unknown variables
7 – No. independent atomic species balances
8 – No. molecular balances on independent nonreactive species
9 – No. other equations relating unknown variables
10 Degrees of freedom
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12 In the ethane dehydrogenation process, the two unknown flow rates will be determined from
13 balances on atomic carbon and atomic hydrogen.

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16 Solving Equations (1) and (2) simultaneously yields
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 Material Balance on the Chemical Reactors 14

1 (c) Extents of reaction.

2 The degree-of-freedom analysis is:
3 No. unknown variables
4 + No. independent reactions (one extent of reaction for each)
5 – No. independent reactive species
6 (One equation for each species in terms of extents of reaction)
7 – No. independent nonreactive species (one balance equation for each)
8 – No. other equations relating unknown variables
9 Degrees of freedom
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11 Example 4.7-1: Below Figure shows a flowchart for the dehydrogenation of ethane in a steady-
12 state continuous reactor.

C2H6 → C2H4 + H2

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14 Molecular Balances

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 Material Balance on the Chemical Reactors 15

1 You could solve for ṅ1 and ṅ2 either directly from the two atomic balances or by using the three
2 molecular species balances.

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5 Guidelines of Solution
6 (a) Molecular species balances require more complex calculations than either of the other
7 two approaches and should be used only for simple systems in involving two reactions.
8 (b) Atomic species balances generally lead to the most straightforward solution procedure,
9 especially when more than one reaction is involved.
10 (c) Extents of reaction are convenient for chemical equilibrium problems and when equation-
11 solving software is to be used.
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13 4.7f Product Separation and Recycle of Unconsumed Reactants

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16 Example:

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𝟕𝟓 − 𝟎
18 𝑶𝒗𝒆𝒓𝒂𝒍𝒍 𝑪𝒐𝒏𝒗𝒆𝒓𝒔𝒊𝒐𝒏 = × 𝟏𝟎𝟎 = 𝟏𝟎𝟎%
𝟕𝟓
𝟏𝟎𝟎 − 𝟐𝟓
19 𝑺𝒊𝒏𝒈𝒍𝒆 − 𝑷𝒂𝒔𝒔 𝑪𝒐𝒏𝒗𝒆𝒓𝒔𝒊𝒐𝒏 = × 𝟏𝟎𝟎 = 𝟕𝟓%
𝟏𝟎𝟎
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 Material Balance on the Chemical Reactors 16

1 Example 4.7-2: Propane is dehydrogenated to form propylene in a catalytic reactor:

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3 The process is to be designed for a 95% overall conversion of propane. The reaction products
4 are separated into two streams: the first, which contains H2, C3H6, and 0.555% of the propane
5 that leaves the reactor, is taken off as product; the second stream, which contains the balance
6 of the unreacted propane and 5% of the propylene in the first stream, is recycled to the reactor.
7 Calculate (a) the composition of the product, (b) the ratio (moles recycled)/(mole fresh feed),
8 and (c) the single-pass conversion.
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10 Solution: Basis: 100 mol Feed

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12 Degree-of-Freedom Analysis

Overall System Mixing Point Reactor Separator.

3 Unknowns 4 Unknowns 5 Unknowns 5 Unknowns

n6, n7, n8 n1, n2, n9, n10 n1, n2, n3, n4, n5 n3, n4, n5, n9, n10
– 2 atomic balances – 2 balances – 2 atomic – 3 balances
(C and H) (C3H8, C3H6) balances (C and (C3H8, C3H6, H2)
– 1 additional relation H) – 2 additional relations
(95% overall propane (n6 = 0.00555 n3 ,
conversion) n10 = 0.05 n7)
0 df 2 df 3 df 0 df
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 Material Balance on the Chemical Reactors 17

1 (a) the analysis of the overall system.

2 95% Overall Propane Conversion (5% unconverted)

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5 (b)

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 Material Balance on the Chemical Reactors 18

1 Example 4.7-3: Methanol is produced in the reaction of carbon dioxide and hydrogen:

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3 The fresh feed to the process contains hydrogen, carbon dioxide, and 0.400 mole% inert (I).
4 The reactor effluent passes to a condenser that removes essentially all of the methanol and water
5 formed and none of the reactants or inert. The latter substances are recycled to the reactor. To
6 avoid buildup of the inert in the system, a purge stream is withdrawn from the recycle.
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8 The feed to the reactor (not the fresh feed to the process) contains 28.0 mole% CO2 70.0 mole%
9 H2, and 2.0 mole% inert. The single-pass conversion of hydrogen is 60.0%. Calculate the molar
10 flow rates and molar compositions of the fresh feed, the total feed to the reactor, the recycle
11 stream, and the purge stream for a methanol production rate of 155 kmol CH3OH/h.
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13 Solution Basis: 100 mol Combined Feed to the Reactor

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15 Degree-of-Freedom Analysis

Overall System Reactor Condenser Mixing Point Splitting Point

7 Unknowns 4 Unknowns 3 Unknowns 5 Unknowns 2 unknowns

nO, xOC, n3, n4, n1, n2, n3, n4 n5, x5C, x5H nO, xOC, nr, nr, np
np, x5C, x5H x5C, x5H
– 5 balances – 4 balances – 3 balances – 3 balances – 1 balance

CO2, H2, I, CO2, H2, CO2, H2, I CO2, H2, I

CH3OH, H2O CH3OH, H2O
3 df 0 df 0 df 2 df 1 df

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 Material Balance on the Chemical Reactors 19

1
2 Solution Procedure
3 • Write balances on the reactor, then the condenser, and then mixing point, and finally the
4 splitting point.
5 • Fowchart may then be scaled up by the required amount to obtain a methanol production
6 rate of 155 kmol/h.
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 Material Balance on the Chemical Reactors 20

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 Material Balance on the Chemical Reactors 21

1 The mole fractions remain unchanged by the scaling. The results follow

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