MATERIAL BALANCES WITH CHEMICAL REACTIONS Introduction: Chemical reactions play a vital role in manufacturing process.

For design of chemical process equipment, the operating conditions such as pressure, temperature, composition and flow of the streams should be known. The material balance and energy balance calculations come to the rescue of the designer and allows him to calculate the various flow rates and temperature of the streams. Assuming that the kinetic data of the reaction is available, the overall material balance of the steady state condition will be discussed here. Material balances: The general mathematical statement can be written as Total mass entering the unit = Total mass of products leaving the unit It should be noted that in chemical reactions, the total mass of the input remains constant, but the total moles may or may not remain constant. Example: Consider the shift reaction CO +H2O CO2 +H2 In this, it can be observed that two moles of reactants react with each other and produce also two moles, thus the number of moles of the reactants entering the reaction equals the number of the products leaving the reaction. The ammonia synthesis reaction can be written as N2 +3H2 2NH3 It can be observed that four moles of reactant only produce two moles of ammonia. The total mass of the reactant entering and the product leaving the reaction are equal. For the reaction of first type

1 mole CO

1 mole H2O 1 mol H2 1 mole CO2

Similarly for second type reaction 1 mole of N2 3 mole of H2 2 mole of NH3 The above equalities decide the stoichiometric requirements of the components. In the processes involving chemical reaction, the total mass of various compounds entering a reaction is equal to the total mass of various components leaving the reaction, but entering moles of components need not be equal to the moles of components leaving. While doing material balance calculations in such case, it is very convenient to use basis of calculations in molar units. Generally calculations should be based on limiting reactant and quantity of new products formed should be calculated with the help of chemical reactions and amount of limiting reactants reacted. For any reactant material the balance of material can be written as Material entering= material reacted +material un reacted For products we can write Material leaving = material produced by the reaction. If the material is produced by more than one reaction, then the material leaving is sum of the materials produced by all he reactions. Definitions: Stoichiometry: It is a theory of the proportions in which chemical species combine with one another.

Stoichiometric equations: Stoichiometric equation of a chemical reaction is a statement indicating relative moles of reactant and products that take part in the reaction. Any balanced reaction equation is a stoichiometric equation. For example consider the stoichiometric equation CO + 2H2 CH3OH

According to the equation one molecule (mol or kmol) of CO reacts with two molecules (mol or kmol) of hydrogen to produce one molecule (mol or kmol) of methanol. Stoichiometric co-efficient: It is the number that precedes the formula of each component involved in a chemical reaction. Thus in the above example, the Stoichiometric co-efficient of CO is one. The stoichiometric co-efficient of H2 is 2 and stoichiometric co-efficient of methanol is one. The stoichiometric requirements of components are given as 1kmol of CO 1kmol of CH3OH 2kmol of H2 Stoichiometric ratio: Two reactants A and B are said to be present in Stoichiometric proportions if the ratio of moles of A present to the moles of B present is equal to the Stoichiometric ratio obtained from the balanced equation. Consider a reaction CO + 2H2 CH3OH

For the reactants in the above equation to be present in Stoichiometric proportion there must be 2 moles of H2 for every mole of CO (then nH2/ n CO = 2/1 = 2) present in the feed to the reactor. When the reactants are fed to a reactor in Stoichiometric proportion and the reaction goes to completion all of the reactants will be consumed. In case of above cited reaction, for example, if 200 kmol of H2 and 100kmol of CO are initially present, the H2 and CO would disappear at the same instant. It follows that if we start with 100ml of CO and less than 200 mol of H2 (i.e., of H2 is present in less than its Stoichiometric proportion) H2 disappears before the CO. On the other hand, if there are more than 200 moles of H2 initially present, the CO disappears first.

Limiting reactant / component: Limiting reactant is the reactant which is present in such proportions that its consumption will limit the extent to which the reaction can proceed. This reactant will not be present in excess of that required to combine with any of the other reacting materials. It is the reactant which is present in such proportion that its compete consumption by the reaction will limit the extent to which the reaction can proceed. It is the reactant that would disappear first if a reaction goes to completion. Excess Reactant: Excess reactant is the reactant which is taken more than the requirement to combine with other reactant as per the Stoichiometry. It is the reactant which will be present in the product even if the reaction goes to completion. It is the one which is in excess of theoretical or stoichiometric requirement. E.g.: Consider the reaction C2H4 + O2 C2H4O

In industrial practice of producing ethylene oxide by oxidation of ethylene, oxygen/ air fed to the reactor is always in excess of theoretically required, thus ethylene is a limiting reactant and oxygen/air is an excess reactant. When all reactants are present in Stoichiometric proportion then none of the reactants involved is limiting. Percentage excess: Percentage excess reactant is defined as % excess quantity taken based on theoretical requirement. It is the amount in excess of Stoichiometric (theoretical) requirements expressed as the percentage of Stoichiometric / theoretical requirement. Consider a reaction A+B Where B is the excess reactant, then Percent excess of B = mole of B supplied or fed moles of B theoretically required x100 Moles of B theoretically required Moles of B theoretically required are the moles of B that would correspond to the stoichiometric proportions. The above formula can be rearranged to calculate quantity of excess reactant actually supplied. Moles of B actually fed = stoichiometric requirement x (1 + fraction of excess of B) The quantity of excess reactant must be found based on quantity of limiting reactant fed to the reactor. Consider for example, the reaction SO2 + 1/2O2 SO3 C

And suppose that 100 moles SO2 /hr and 75 moles O2 /h are fed to the reactor. SO2 is clearly the limiting reactant and to be in stoichiometric proportions, moles of O2 would have to be 50 kmol / hr. The percent excess of O2 is therefore = [(75 50) / 50] x 100 = 50

CONVERSION: Conversion or fractional conversion or degree of completion is defined with respect to limiting reactant and it gives idea regarding degree of completion of reaction. The unreacted quantities of raw materials are easily obtained knowing the charged quantities with the help of conversion then in turn it gives idea in case of unit process whether recycling is to be done or not for process to be economically feasible. Consider a chemical reaction A+B Where A = a limiting reactant B = the excess reactant. Then the conversion or fractional conversion of A is the ratio of amount of A reacted to the amount of A charged or fed to a reactor. The percentage conversion of A is the amount of A reacted expressed as the percentage of amount of A charged or fed to a reactor. The amount of A can be expressed in moles or weight of the amount of A is expressed in moles then % conversion of A = Moles of A reacted Moles of A charged or fed In case of recycle operations, the term namely per pass conversion is commonly used. The per pass conversion is defined as the quantity of limiting reactant reacted / consumed expressed as a percentage of limiting reactant in the mixed feed. If 100 moles of a reactant are fed and 75 moles of the reactant reacts, the fractional conversion is 0.75 (the % conversion is 75%) and the fraction unreacted is 0.25. If 50 moles of a reactant are fed and the percentage conversion is 80% then (50) x0.8 = 40 moles have reacted and (50) (0.20) = 10 moles remain reacted. YIELD and SELECTIVITY: In most of the chemical processes, though the objective is to produce a desired product by reacting raw materials, the raw material may also undergo a series of parallel reactions (side reaction) resulting into production of undesired material which has reverse effect on economics of the process. In such cases, in industrial practice, the steps are taken to depress the side reaction by use of selective catalyst or by other x 100 C

means like maintaining proper concentration of reactants and by varying the temperature of reaction. In addition the inhibitors are also used. The terms yield and selectivity are used in case of multiple reactions to give information regarding the degree to which a desired reaction predominates over side reaction or reactions involved. Consider the multiple reactions, namely a series parallel reaction, a series reaction and a parallel reaction Series parallel reaction A+B C+B Series reaction Parallel reaction A A A Then yield of C is given as Yield of C = moles of A reacted to produce C Total moles of A reacted Yield of desired product is the quantity of limiting reactant reacted to produce the desired product. It is expressed as a percentage of quantity of limiting reactant reacted totally to produce the desired product . Consider parallel reaction A C and A D Where C is a desired component, D is an undesired component In such cases, the selectivity is given as Selectivity of C relative to D = UNIT PROCESSES: A Unit Process is a step in manufacturing in which chemical reaction takes place like oxidation of toluene to benzaldehyde, hydrogenation of oils to vanaspathi. Following are some of the examples of unit processes moles of C (desired product) formed Moles of D (undesired product) formed x 100 C C D C D D

Where C is a desired product, D is an undesired product, A is a limiting reactant.

Oxidation, hydrogenation, nitration, hydrolysis, esterification, Neutralization, alkylation, amination etc. OXIDATION: Oxidation is defined in many ways and one simple definition of oxidation is the interaction between oxygen molecules and all the different substances they may contact CH3CHO Acetaldehyde C6H6 Benzene 4HCl HYDROGENATION: This unit process specifically refers to the chemical reaction of a substance with molecular hydrogen in the presence of a catalyst. CO2 NITRATION: Those reactions where one or more nitro group (- NO2)n are introduced into the reacting molecule. CH3 C6H5 CH3 + HNO3 C6H4 NO2 Toluene HYDROLYSIS: It is applied to the reaction where in water effect a double decomposition with another compound, hydrogen going to one component hydronyl to other. C5H10Cl2 Mono chloro pentane + H2O HCl + C5H11OH n pentanol hydro chloride nitric acid mono nitro toluene + H2O + 3H2 CH3OH + H2O R CH = CH R' + H2 RCH2 CH2 R' + O2 + + 1/2O2 oxygen 1/2O2 CH3COOH Acetic acid C4H2O3 2Cl2 + + 2CO2 2 H2O + 2H2O maleic anhydride

KCN Pot.cyanide NEUTRALISATION:

H2O

HCN

KOH pot.hydroxide

hydrogen cyanide

The reaction taking place between an acid and alkali resulting in the formation of salt and water is called neutralization. CH3COOH Acetic acid ALKYLATION: It may be defined as introduction of alkyl radical by substitution or addition into an organic compound. CH3Br + 2Na sodium + C2H5Br CH3C2H5 propane + 2NaBr sodium bromide Methyl bromide AMINATION: The amination reaction is one which results in the formation of amines. This may be by reduction or by ammonolysis Amination by reduction: It refers to those reactions which involve the synthesis of amines by reductive methods. Amines may be defined as derivatives of ammonia where one or more of the hydrogen is replaced by alkyl, aryl, hydronyl, aralkyl or heterocyclic groups. NO2 Zn Acid Nitro benzene aniline NH2 ethyl bromide + NaOH sodium hydroxide CH3COONa sodium acetate + H2O

Amination by ammonolysis: It is the process of forming amines by the action of ammonia. It also includes the use of the primary and secondary amines as aminating agents. H2 RCHO + NH3 SULFONATION: It may be defined as any chemical processes by which the sulfonic acid group (SO2OH) or the corresponding salt or sulfonyl halide group (- SO2Cl) is introduced into an organic compound. R CH2COOH NH2COOH + + SO3 H2S2O7 R CH (SO2OH) COOH NH2SO3H + CO2 R CN (H2O + H2) RCH2 NH2

EMULSIFICATION: All chemical reactions resulting in the formation of esters are all under this category. CH3COOH Acetic acid + CH3CH2OH n-propanol CH3COOC2H5 ethyl acetate + H2O water

HALOGENATION (Chlorination): It can be defined as the process where by one or more halogen atom is introduced into an organic compound. C6H6 Benzene C6H5Cl + Mono chloro benzene CH2 = CH2 Ethylene + + Cl2 chlorine Cl2 chlorine Br2 bromide C6H5Cl C6H4Cl2 + + HCl HCl mono chloro benzene dichlorobenzene CH2Br - CH2Br ethylene bromide

Oxidation reactions: Note: Air is used as source of oxygen Air is a mixture of oxygen and nitrogen Air contains 79% nitrogen and 21% oxygen by mole Solution Procedure: Assume a suitable basis Write the possible reactions Calculate the oxygen required assuming complete oxidation Calculate oxygen supplied from the excess Calculate nitrogen entering along with oxygen Identify the products of oxidation for the problem Calculate the quantities of each of the products Calculate the other required quantities as per problem requirement 1. Ethylene oxide is produced by oxidation of ethylene. 100 kmol of ethylene are fed to a reactor and the product is found to contain 80 kmol ethylene oxide and 10 kmol CO2. Calculate a) the % conversion of ethylene and b) the percent yield to ethylene oxide. Basis: 100 kmol ethylene fed to the reactor. Reactions: C2H4+1/2 O2 C2H4O (1) C2H4+3O2 2CO2+2H2O (2) 80 kmol ethylene oxide is produced and this is possible only by reaction 1. As per Stoichiometry 1kmol ethylene oxide will be produced per kmol of ehylene. Therefore ethylene reacted for reaction 1 is 80 kmoles.

10 kmol of CO2 is produced and this possible through reaction 2. As per Stoichiometry 2 moles CO2 will be produced per mol ethylene. Therefore kmol ethylene reacted by reaction 2 is 10/2=5 kmol. Total ethylene reacted towards equation1and 2 = 80 + 5 = 85 kmol. Total kmol of ethylene taken = 100 kmol Therefore % conversion = (ethylene reacted / ethylene taken) x100 = (85/100) x100= 85% % yield of ethylene oxide= (moles ethylene reacted to ethylene oxide /Total moles of ethylene reacted) x100 = (80/85)100=94.12% 2. In the production of chlorine gas by oxidation of hydrochloric acid gas, air is used 30% in excess of that theoretically required. Based on 4 kmol HCl, Calculate a) the weight ratio of air to hydrochloric aid gas in feed. b) if the oxidation is 80% complete, find the composition of the product stream on mole basis. Basis: 4 kmol HCl 4HCl+ O2 O2 required = 1 kmol O2 supplied= 1x1.30 = 1.3 kmol because 30% excess air is used N2 supplied along with O2= 1.3 x 79/21=4.89 Air supplied= O2 supplied + N2 supplied= 1.3+4.89=6.19 kmol Weight of air supplied= 6.19x29=179.51 kg HCl taken= 4 kmol= 4x36.5= 146 kg Weight ratio of air to hydrochloric acid in feed = 179.51/ 146=1.23 If oxidation is 80% complete composition of the gases in mole% Gases leaving: Cl2, H2O, HCl,O2, N2 HCl reacted= 4x0.8=3.2 kmol HCl leaving unreacted= 4 - 3.2=0.8 kmol 2Cl2 + 2 H2O

O2 leaving = O2 supplied O2 consumed= 1.3 3.2x1/4 =1.3-0.8= 0.5kmol N2 leaving = N2 entering= 4.89 kmol Cl2 leaving = Cl2 produced= 3.2x2/4= 1.6 kmol H2O leaving = H2O produced= 3.2x2/4= 1.6 kmol Composition of gases leaving:

Components Cl2 H2O HCl O2 N2 Total

Kmoles 1.60 1.60 0.80 0.50 4.89 9.39

Mole% 17.04 17.04 8.52 5.32 52.08 100.00

3. Calculate the composition of gases obtained by the burning of pure FeS2 with 60% excess air. The oxidation proceeds according to the reaction 4FeS2 +11O2 Assume complete conversion of the reaction Basis: 4 kmol of FeS2 O2 required= 11 kmol O2 supplied =11x1.6= 17.6 kmol N2 supplied= 17.6x79/21=66.21 kmol Gases leaving: SO2,O2,N2 SO2 leaving = SO2 produced= 8 kmol 2Fe2O3 + 8 SO2 .

O2 leaving= O2 supplied- O2 utilized= 17.6- 11 =6.6 moles (O2 required= O2 utilized because of complete conversion of reaction) N2 leaving = N2 supplied=66.21kmol Composition of gases leaving:

Component SO O N
2

moles 8.00 6.60 66.21 80.81

Mole% 9.90 8.17 81.93 100.00

Total

4. Iron pyrites FeS2 is burnt with air 100 % in excess of that required to oxidize all iron to Fe2O3 and all sulphur to sulphur dioxide. Calculate the composition of the exit gases in mole% and weight %, if 80% of sulphur is oxidized to sulphur dioxide and the rest to sulphur trioxide. All iron is oxidized to Fe2O3. Basis: 4 moles of FeS2 4FeS2 +11O2 2Fe2O3 + 8 SO2 SO3

SO2 +1/2O2 O2 required= 11 moles O2 supplied =11x2= 22 moles N2 supplied= 22x79/21=82.76 moles Gases leaving: SO2, SO3,O2,N2

SO2 leaving= SO2 produced- SO2 converted to SO3 = 8 8 x(1-0.8) = 8 -1.6 = 6.4 moles SO3 leaving = SO3 produced= 1.6 moles O2 leaving = O2 supplied O2 consumed = 22 - 11- (1.6 x1/2 ) = 22-11- 0.8 =10.2

N2 leaving = N2 supplied= 82.76 moles Compositions of gases leaving Component SO SO O N

2

Moles 6.40 1.60 10.20 82.76 100.96

Mole% 6.34 1.58 10.10 81.97 99.99

Mol.wt 64 80 32 28

weight 409.46 128.00 326.40 2317.28 3181.14

Weight% 12.87 4.02 10.26 72.84 99.99

Total

5. Orthoxylene on oxidation gives Phthalic anhydride as per the reaction C8H10 +3O2 C8H4O3+3H2O. 20% excess air is used. Conversion is 50% and yield of phthalic anhydride is 90%.Calculate the requirement of orthoxylene and air for 100 kmole of phthalic anhydrid Basis: 1 mol orthoxylene C8H10 +3O2 C8H10+21/2 O2 C8H4O3+3H2O 8CO2+5H2O

O2 required= 3 kmol O2 supplied=3x1.2= 3.6 kmol N2 supplied= 3.6x79/21=13.54 kmol From Stoichiometry kmol phthalic anhydride produced assuming 100% yield= 0.5 kmol Since yield is 90%, phthalic anhydride produced=0.5x0.9=0.45 kmol To produce 0.45 kmol phthalic anhydride , kmol of orthoxyene used = 1 kmol Therefore to produce 100 kmol phthalic anhydride, orthoxylene required= (1/0.45)x100=222.22 kmol Weight of orthoxylene required= 222.22x106=23555.55 kg.

6. In the oxidation of SO2 to SO3, the conversion is 75% by using 70% excess air. Calculate a) composition of gases leaving the reactor in mole basis b) kg mole air fed per kg mole SO2. Basis: 1mol SO2 SO2+1/2O2 Mol O2 required= 0.5 mol O2 supplied= 0.5x1.7= 0.85 N2 supplied=0.85x79/21=3.20 Air supplied= O2 supplied +N2 supplied= 0.85+3.2=4.05 Gases leaving the reactor SO2,SO3,O2,N2 Moles SO2 reacted=1x0.75= 0.75 kmol Moes SO2 leaving = SO2 unreacted= 1x(1-0.75)=0.25 Moles SO3 leaving = mol SO3 produced= 0.75x1/1=0.75 Mol O2 leaving= mol O2 supplied-O2 consumed = 0.85-0.75x1/2= 0.85-0.375=0.475 Mol N2 leaving= mol N2 supplied= 3.20 Composition of gases leaving Component SO2 SO3 O2 N2 Total Mol 0.250 0.750 0.475 3.200 4.675 Mol% 5.35 16.04 10.16 68.45 100.00 SO3

7. In production of sulphur trioxide (SO3) 100 k mol of SO2 and 200 k mol of O2 are fed to the reactor. The product stream is found to contain 80 k mol of SO3. Find the percent conversion of SO2. BASIS: 100 k mol of SO2 entering the reactor 100 k mol of SO2 200 k mol O2 REACTOR product SO3, SO2 ,O2

Reaction 1 k mol of SO2

SO2 + 1/2O2 1 k mol of SO3

SO3

1 k mol SO3 requires 1 k mol of SO2 to be reacted by above reaction 1 k mol of SO3 80 k mol of SO3 = SO2 reacted = 80 x (1/1) = 80 k mol % conversion of SO2 = k mol of SO2 reacted * 100 = 80 * 100 = 80% K mol of SO2 fed 100 1 k mol of SO2 ?

8.10 kg of PbS and 3 kgs of O2 react to yield 6 kgs of Pb and 1 kg of PbO2 according to the reaction PbS + O2 PbS+2O2 Pb+ SO2 PbO2+SO2

Calculate a. the amount of PbS that does not react b. %excess O2 based on the amount of PbS that actually reacts c. amounts of SO2 formed d. % conversion of PbS to Pb. Basis: 10 kg PbS and 3 kg O2 taken PbS + O2 PbS+2O2 PbO2= 239.2 SO2=64, O2=32 , 2O2=64 Pb+ SO2 ( 1) PbO2+SO2 (2)

The atomic weight values are Pb-207.2, S-32, O-16. Therefore weights of PbS = 239.2, Pb leaving= 6 kg = Pb produced according to reaction 1. PbS reacted for reaction 1 = (239.2/ 207.2)x6= 6.93 kg PbS reacted for reaction 2= (239.2/239.2)x1= 1 kg Total PbS reacted= 6.93+1=7.93 kg Amount of PbS that does not react= 10-7.93= 2.07 kg O2 required= (32/239.2)6.93 + (64/239.2)1=0.927+0.268=1.195 O2 taken =3 kg % excess O2= [(O2 taken O2 required)/ O2 required] x100

= [(3-1.195) / 1.195] x 100 = 151.05% SO2 formed by reaction 1= (64/207.2) x 6.93 = 2.14 SO2 formed by reaction 2 = (64/207.2) x 1 = 0.31 Total SO2 formed= 2.14+0.31=2.45 kg Conversion of PbS to Pb = (PbS reacted to Pb / PbS taken) x100 = (6.93/10) x100 = 69.3%. 9. Vapor phase oxidation of ethyl alcohol using Cu catalyst at 550 C results into formation of acetaldehyde C2H5OH + 1/2O2 CH3CHO + H2O

The conversion is 30% and excess air used is 10%. Calculate the composition of product stream if 100 kg of C2H5OH per hour is fed to the reactor. BASIS: 1 hr operation 100 kg/hr of C2H5OH is fed which is equal to = 100/46 = 2.1739 k mole O2 required for 2.1739 k mole of C2H5OH = 2.1739x1/2 =1.087 O2 supplied = 1.087 x 1.1 = 1.1957 k mole N2 accompanying = 1.1957 x (79/21) = 4.4981 k mole Quantity of aldehyde formed = 2.1739 x 0.3 = 0.6522 (the conversion is 30%) Alcohol (C2H5OH) remaining unconverted = supplied consumed = 2.1739 (2.1739 x 0.3) = 1.5217 k mole Water formed during the reaction = 0.6522 k mole Oxygen leaving= oxygen supplied- oxygen utilized =1.1957-2.1739x0.3x0.5=1.1957-0.3261=0.8696 kmol Nitrogen leaving= 4.4981 kmol Component Alcohol Formaldehyde Water Oxygen Nitrogen Moles 1.5217 0.6522 0.6522 0.8696 4.4981 8.1938 Mole% 18.57 7.96 7.96 10.61 54.90 100.00

10. Ethylene and oxygen are fed to a tubular reactor filled with silver catalyst at 250 C. The product ethylene oxide is recovered from gaseous effluent by absorption in water in presence of acid at 60 C. The reaction taking place is as follows C2H4 + 1/2O2 C2H4O + H2O C2H4O CH2OH CH2OH Conversion for reaction (1) is 90% which for reaction (2) it is 65%. If 100 kg of ethylene glycol (CH2OH - CH2OH) is formed, Calculate the quantity of ethylene supplied to the tubular reactor. BASIS: 100 kg of CH2OH - CH2OH formed Ethylene glycol formed= 100/62 = 1.6129 k mol As per reaction (2) the conversion is 65% Quantity of C2H4O required for 1.6129 k mole of (CH2OH) 2 will be = 1.6129 x1/1x (100/65)= 2.4814 k mol As per reaction (1) conversion is 90% Quantity of C2H4 required for the formation of 2.4814 k mole of C2H4O will be = 2.4814 x (100/90) = 2.757 kmol Mass of C2H4 required = 2.757 x 28 = 77.196 kg Mass of C2H4 required for 100 kg of ethylene glycol formed is 77.196 kg. 11. Ethylene oxide is produced by oxidation of ethylene .100 k mole of ethylene and 100 k mole of oxygen is charged to the reactor. The conversion of ethylene is 85% and percent yield of C2H4O is 94.12.Calculate the composition of product leaving the reactor. BASIS: 100 k mol each of C2H4 and O2 charged 100 k mole of C2H4 100 k mole of O2 REACTOR Product C2H4, C2H4O, CO2, H2O - (1) - (2)

C2H4 + 1/2O2 C2H4 + 3O2 Percent conversion = 85

C2H4O 2CO2 + 2H2O

Moles of C2H4 totally reacted = 0.85 x 100 = 85 k mol Percent yield of C2H4O = 94.12 Moles of C2H4 reacted to C2H4O by reaction (1) = 0.9412 x85 = 80 kmol Moles of C2H4 reacted by reaction (2) = 85 80 = 5 k mole 1 kmol C2H4 2 kmol of CO2 Moles of CO2 produced = (2/1) x 5 = 10 k moles From reaction 1, 1 kmol of C2H4 0.5 k mol O2 O2 reacted by reaction 1 = (0.5/1) x 80 = 40 kmol From reaction 2, 1 k mol C2H4 3 kmol of O2 O2 reacted by reaction 2 = (3/1) x 5 = 15 k moles O2 totally reacted = 40 + 15 = 55 k moles O2 fed = O2 reacted + O2 unreacted O2 unreacted = 100 55 = 45 kmoles 1 kmol of C2H4 2 kmol of H2O Moles of H2O produced = (2/1) x 5 = 10 kmoles C2H4 fed = C2H4 reacted + C2H4 unreacted C2H4 unreacted = 100 85 = 15 kmoles Composition of product stream: Component C2H4 C2H4O O2 CO2 H2O Total Quantity, kmol 15 85 45 10 10 160 Mole% 9.38 50.00 28.12 6.25 6.25 100.00

12. Oxidation of ethylene to produce ethylene oxide is given by reaction C2H4 + 1/2 O2 C2H4O

If air is used 20%b in excess of that theoretically required. Calculate the quantity of air supplied based on 100 k mol of ethylene fed to the reactor. BASIS: 100 kmol of ethylene fed to the reactor. Reaction: C2H4 + 1/2 O2 C2H4O

From reaction we have 1 kmol of C2H4 0.5 kmol of O2

Stoichiometric or theoretical requirement of oxygen for 1 kmol of C2H4 Theoretical requirement of oxygen for 100 kmol of C2H4 = (0.5/1) x 100 = 50 k moles Oxygen supplied 20% in excess of theoretical requirements, Oxygen in supplied air = theoretical requirement of oxygen = 50 x 1.2= 60 kmol Moles of air supplied = (100/21)x 60 = 285.71 kmoles Amount of air supplied = 285.71 x 29 = 8285.59 kg 13.In manufacture of acetic acid by oxidation of acetaldehyde, acetaldehyde and oxygen were fed to reactor and the product leaving the reactor contains 14.81% acetaldehyde, 59.26% acetic acid and rest oxygen (mole basis). Find the % conversion of acetaldehyde. 0.5 kmol of O2

BASIS: 100 k mol of products leaving Acetaldehyde Oxygen REACTOR Acetic acid- 59.26% acetaldehyde-14.81% Oxygen-25.93 Reaction: CH3CHO + 1/2O2 CH3COOH

Acetic acid formed= 59.26 kmoles Acetaldehyde reacted= 59.26x1/1= 59.26 kmol Acetaldehyde unreacted= 14.81 kmol Total acetaldehyde entering= reacted +unreacted= 59.26+14.81= 74.07 kmol % conversion of acetaldehyde= (59.26/ 74.07) x100= 80% 14. In production of sulphur trioxide, 100 k mol of SO2 and 100 k mol of O2 are fed to the reactor. If the % conversion of SO2 is 80, calculate the composition of the product stream on mole basis BASIS: 100 k mol of SO2 and 100 k mole of O2 charged to the reactor 100 k mol of SO2 100 Kmol of O2 REACTOR REACTOR Product SO3, SO2, O2 Reaction SO2 + 1/2O2 SO3

Percent conversion = 80% Moles of SO2 reacted = 100x0.8= 80 kmol SO2 unreacted = 100 80 = 20 k mol From reaction From reaction 1 k mol of SO2 k mol of O2 1 k mole of SO2 1 k mole of SO3 SO3 produced = (1/1) x 80 = 80 k mol

O2 reacted = (0.5 / 1) 80 = 40 k molx O2 unreacted = 100 40 = 60 k mol Composition of product stream Component SO2 SO3 O2 Total k mol 20 80 60 160 mole% 12.5 50.0 37.5 100.0

15. In manufacture of SO3,the feed to the reactor consists of 50 k moles of SO2 and 150 k moles of air. Calculate % excess of air used. BASIS: 50 k moles of SO2 fed to the reactor. Reaction: SO2 + 1/2 O2 SO3

Air used = 150 k mole Oxygen in supplied air = 150 x 0.21 = 31.5 kmol From reaction 1 kmol of SO2 0.5 kmol of O2 = (0.5/1) x 50 = 25 kmol % excess O2 used = oxygen supplied oxygen theoretically required Oxygen theoretically required = [(31.5 25) / 25] x100 = 26 16.In the manufacture of benzaldehyde a mixture containing dry air and toluene is fed to the reactor (converter) at a temperature of 448 K (175 C) and 100 kpa of pressure. The mixture passes through the catalyst bed in the converter. The product gas stream leaves the converter at 468 K (195 C). The reaction takes place as follows Theoretical (stoichiometric) requirement of O2 for 50 kmol SO2

C6H5CH3 (g) + O2 (g)

C6H5CHO (g) + H2O (g)

The dry air is supplied at 100% excess so as to maintain the high yield of benzaldehyde. The side reaction taking place is C6H5CH3 (g) + 9O2 (g) 7CO2 (g) + 4H2O (g)

At the above mentioned conditions the overall conversion is 13% based on toluene. Approximately 0.5 of the toluene charged burns to CO2 and H2O. calculate the composition of gas stream leaving the converter. BASIS: 100 kmol of toluene charged C6H5CH3 (g) + O2 (g) C6H5CH3 (g) + 9O2 (g) Overall conversion = 13% Toluene totally reacted = 0.13 x 100 =13 kmol Toluene unreacted = 100 13 = 87 kmol Toluene Air C6H5CHO, C6H5CH3, CO2, H2,N2 C6H5CHO (g) + H2O (g) 7CO2 (g) + 4H2O (g)

Toluene reacted by reaction 2 = (0.5/100) x 100 = 0.5 kmol Toluene reacted by reaction 1 = 13 0.5 = 12.5 kmol From reaction 1 kmol of toluene 1 kmol of benzaldehyde 1 kmol of water Benzaldehyde produced = (1/1) x 12.5 = 12.5 kmol Water produced by reaction 1 = (1/1) x 12.5 = 12.5 kmol Carbon dioxide produced by reaction 2 = (7/1) x 0.5 = 3.5 kmol Water produced by reaction 2 = (4/1) x 0.5 = 2 kmol

Total water produced = 12.5 + 2 = 14.5 kmol Theoretical oxygen required = (1/1)x 100 = 100 kmol Oxygen in supplied air = 100 x2 = 200 kmol (100% excess ) Nitrogen in supplied air = 200 x 79 /21 = 752.4 kmol Oxygen reacted = oxygen reacted by reaction 1 + oxygen reacted by reaction 2 = (1/1) x 12.5 + (9/1)x 0.5 = 17 kmol Oxygen unreacted = 200 17 = 193 kmol Component C6H5CH3 C6H5CHO N2 O2 CO2 H2O kmol 87.0 72.5 752.4 193.0 3.5 14.5 1062.9 Hydrogenation 17.A mixture of pure carbon dioxide and hydrogen is passed over a nickel catalyst. The temperature of the catalyst bed is 588K and the reactor pressure is 2.02 mPag. The gas mixture leaving the reactor is analyzed to contain 57.1% CO2, 41.1% H2, 1.68% CH4 and 0.12% CO by volume on dry basis. The reactions taking place in the reactor are CO2+4H2 CH4+2H2O CO2+H2 CO+H2O Find a) the conversion of CO2 per pass b) the yield of CH4 in terms of CO2 reacted and c) the composition of feed. Basis: 100 kmol of dry gases leaving the reactor CO+4H2 CH4+2H2O (1) CO2+H2 CO+H2O (2) mole% 8.18 1.18 70.79 18.16 0.33 1.36 100.00

Methane leaving = 1.68 kmol Therefore CO2 reacted by equation 1= 1/1x1.68= 1.68 kmol Co leaving =1.2 kmol Therefore CO2 reacted by equation 2= 1/1x0.12= 0.12 kmol Total CO2 reacted = 1.68+0.12= 1.8 kmol CO2 supplied= CO2 reacted + CO2 un reacted = 1.8 + 57.1= 58.9 kmol % conversion of CO2 per pass= (1.8/58.9)x100= 3.056 % % yield of CH4 = (kmol CO2 reaced to CH4/ kmol CO2 totally reacted) x100 = (1.68/1.8)x100=93.33 Hydrogen reacted by equation 1= 4/1x1.68= 6.72 kmol H2 reacted by reaction 2= 1/1x0.12= 0.12 Total hydrogen reacted= 6.72 + 0.12 = 6.84 Hydrogen supplied= hydrogen reacted + hydrogen un reacted = 6.84+41.1= 47.94 kmol Analysis of feed Component H2 CO2 Total Mol 47.94 58.90 106.84 Mol% 44.87 55.13 100.00

18.Gaseous benzene C6H6 reacts with hydrogen in presence of Ni catalyst as per the reaction C6H6 + Benzene 3H2 C6H12 cyclohexane

30% excess hydrogen is used above that required by the above reaction. Conversion is 50% and yield is 90%. Calculate the requirement of benzene and hydrogen gas for 100 moles of cyclohexane. Basis: 1 mol benzene H2 required= 3 mol Hydrogen supplied= 3x1.3= 3.9 mol Cyclohexane produced for a 50% conversion and 100 % yield= (1/1) x 1 x 0.5 = 0.5 mol Since yield is 90 %, cyclohexane produced = 0.5 x 0.9 = 0.45 mol

0.45 mol cyclohexane is produce by 1 mol hexane Therefore mole hexane required t produce 100 mole cyclohexane= (1/0.45) x100 = 222.22 mol Hydrogen supplied to produce 100 mol cyclohexane = (3.9/1)222.22 = 866.658 mol 19.An organic ester of formula C19H36O2 is to be hydrogenated at a rate of 100 kg / hr to yield C19H38O2. The hydrogen required for the plant, which run continuously, is available as 50 lit cylinders in which the gas is contained at 70 bar and 300 K. How many cylinder should the company order per week? Basis: 100 kg / hr of C19H36O2 C19H36O2 + H2 Mol weight of C19H36O2 = 228 + 36 + 32 = 296 Mol weight of C19H38O2 = 228 + 38 + 32 = 298 Mol C19H36O2 charged = 100/ 296 kmol Hydrogen required per hour= (1/1)100/296= 100/296 kmol Volume of hydrogen required= (100/296) 22.414 x 1000 x 300 /273 x1.013 / 70 = 120.42 lit/hr Volume hydrogen required per week= 120.42 x 24 x 7= 20230.56 lit Volume of 1 cylinder= 50 lit Therefore number of cylinders required= 20230.56 / 50= 404.61 20. Methanol is produced by the reaction of carbon monoxide with hydrogen. CO+2H2 CH3OH The side reaction is CO+3H2 CH4+H2O .(2) The conversion per pass is 12.5%.Of this 87.5% is reached via equation (1) and 12.5% reach via equation (2). The feed mixture entering the reactor contains 32 mol% CO and 68 mol% hydrogen. The stream leaving the reactor passes through a condenser and a separator. The carbon monoxide and hydrogen leaving this unit are recycled. The methane leaves as a gas and the liquid mixture of methanol and water passes to a distillation column for the concentration of methanol.Compute a) the analysis of hot gases leaving the reactor by mol% and weight % b)the methanol content weight% of the liquid leaving the condenser. (1) C19 H38O2

Basis: 100 mol feed to the reactor Conversion per pass= 12.5% Gase leaving: CO, Therefore CO consumed = 32 x 0.125 = 4 kmol CO consumed by reaction (1) is = 4 x 0.875 = 3.5 kmol CO consumed by reaction (2) is = 4 x 0.125 = 0.5 kmol Total CO reacted = 3.5 + 0.5 = 4 k mol CO leaving= CO unreacted = CO entering CO reacted= 32- 4 = 28 kmol H2 consumed in reaction (1) = (2/1) 3.5 = 7 kmol H2 consumed in reaction (2) = (3/1)0.5 = 1.5 kmol Total H2 consumed = 7+1.5 = 8.5 kmol H2 leaving = H2 unreacted = H2 supplied H2 consumed = 68 - 8.5 = 59.5 kmol Methanol leaving the reactor= methanol formed = (1/1) x 3.5 = 3.5 kmol Water leaving the reactor = Water formed = (1/1) x 0.5 = 0.5 kmol Methane leaving= methane formed = (1/1) x 0.5 = 0.5 kmol Analysis of gases leaving: Component mol Mol% Mol weight CO H2 CH3OH H2O CH4 Total 28 59.5 3.5 0.5 0.5 92 30.43 64.68 3.81 0.54 0.54 100.00 28 2 32 18 16 784 119 112 9 8 1032 75.97 11.53 10.85 0.87 0.78 100.00 weight Weight%

Methanol content of the liquid =

x100 = 92.56% by weight

21. The carbon monoxide is reacted with hydrogen to produce methanol. Calculate from the reaction, the stoichiometric ratio of H2 to CO. k mol of CH3OH produced per k mol CO reacted. The weight ratios of CO to H2 if both are fed to the reactor in stoichiometric proportions. The quantity of CO required to produce 1000 kg of CH3OH.

reaction

CO + 2H2

CH3OH

Stoichiometric co-efficient of CO = a =1 Stoichiometric co-efficient of H2 = b = 2 Stoichiometric ratio of H2 to CO = b/a = 2/1 = 2 From the reaction 1 k mol of CO CO = feed to the reactor = 100 kg CO = feed to the reactor = 1 * 28 = 28 kg H2 fed to the reactor in stoichiometric proportion with CO = 2 k mol. H2 fed to the reactor = 2 * 2 = 4 Weight ratio of CO to H2 fed = 28/4 = 70 For reaction 28 kg CO 32 kg CH3OH Amount of CO required to produce 1000 kg CH3OH = 28/32 * 100 = 875 kg. 22. Ammonia is produced by following reaction N2 + H2 2NH3 Calculate the molal flow rate of hydrogen corresponding to nitrogen feed rate of 25 k mol/hr if they are at the stochiometric proportions. The kg of ammonia produced per hour if percent conversion is 25 and nitrogen feed rate is 25 k mol/hr. BASIS: 25 kmol / hr of N2 fed to the reactor. Reaction: N2 + H2 2NH3 1 k mol of CH3OH CO reacted to produce 1 k mol of CH3OH = 1/1 * 1 = 1 k mol.

Stoichiometric proportion of N2 to H2 from the reaction is 1:3 1 k mol of N2 3 k mol of H2 Molal flow rate of hydrogen in stoichiometric proportion to nitrogen flow rate = 3/1x25 = 75 k mol/hr No of moles of N2 reacted = 25x0.25 = 6.25 k mol/hr From reaction we have 1 k mol of N2 2 k mol of NH3 2 k mol of NH3 is produced per 1 k mol of N2 reacted NH3 produced = (2/1) x 6.25 = 12.50 k mol/hr

Amount of NH3 produced = 12.5x molecular weight of NH3 = 12.5x 17 = 212.5 kg/hr. 23.Gaseous benzene (C6H6) reacts with hydrogen in presence of Ni catalyst as per the reaction C6H6 (g) + 3H2 (g) C6H12 (g)

30% excess hydrogen is used above that required by the above reaction. Conversion is 50% and yield is 90%. Calculate the requirement of benzene and hydrogen gas for 100 kmol of cyclo hexane. BASIS: 100 kmol of cyclo hexane Reaction: C6H6 (g) + 3H2 (g) C6H12 (g) Cyclo hexane produced = 100 kmol 1 kmol of cyclo hexane needs 1 kmol of benzene Benzene reacted to cyclo hexane = 1/ 1x100 =100kmol % yield of cyclo hexane = kmol of benzene reacted to produce cyclo hexane x100 kmol of benzene totally reacted 90 = 100 x 100 Kmol of benzene totally reacted Kmoles of benzene totally reacted = 100 x 100 = 111.11 kmol 90 % conversion of benzene = 50 % conversion of benzene = kmol of benzene totally reacted x 100 Kmol of benzene totally fed 50 = 111.11 x 100 Kmol of benzene charged Kmol of benzene charged = 100 x 111.11 = 222.22 kmol 50 From reaction 1 kmol of benzene 3 kmol of hydrogen Theoretical requirement of hydrogen gas = 3/1x 222.22 = 666.66 kmol Requirement of benzene = 222.22 kmol Requirement of hydrogen = 666.66 kmol

Nitration 24.Benzene reacts with nitric acid to produce nitrobenzene and water C6H6+HNO3 C6H5NO2 +H2O Nitrobenzene undergo further nitration to form dinitrobenzene C6H5NO2 +HNO3 C6H4 (NO2)2+H2O The percent conversion of benzene is 90 and acid used is 65% excess over theoretical required by reaction 1. If the mole ratio of benzene to dinitrobenzene in product stream is 17:1, calculate the quantities of benzene and nitric acid required for production of 2000 kg/h of nitrobenzene. Basis: 1kmol / h benzene fed to the reactor C6H6+HNO3 C6H5NO2 +H2O C6H5NO2 +HNO3 C6H4 (NO2)2+H2O Benzene converted= 0.9 kmol because conversion is 90% Kmol nitrobenzene produced = 0.9 x 17/18= 0.85 Kmol dinitrobenzene produced= 0.9 x 1/18= 0.05 (Ratio of nitrobenzene to dinitrobenzene in product is 17:1) Nitric acid required for the reaction= 1kmol Nitric acid fed = 1 x 1.65 = 1.65 kmol Weight of Nitric acid fed = 1.65 x 63 = 103.95 kg/h Weight of benzene fed to the reactor = 1x78= 78 kg/h Nitrobenzene produce /h = 0.85 x 123 = 104.55 kg/h Benzene required for the production of 2000 kg/h of nitrobenzene = (78/104.55) x 2000 = 1492.11kg/h Nitric acid required for the production of 2000 kg/h of nitrobenzene = (103.95/104.55) x 2000 = 1988.52 kg/h 25. Benzene reacts with nitric acid to produce nitrobenzene and water. Some of the nitrobenzene may further undergo nitration to form dinitrobenzene. If the product streams contain 10 mol nitrobenzene,2 mol dinitrobenzene and 4mol benzene, calculate the percent conversion of benzene, yield of nitrobenzene and selectivity to nitrobenzene.

Basis: 10 mol nitrobenzene, 2 mol dinitrobenzene and 4 mol benzene in the product stream C6H6+HNO3 Benzene reacted to give nitrobenzene Benzene reacted to give dinitrobenzene Total benzene reacted= 10+2 =12 mol Benzene unreacted = 4 mol Benzene charged = benzene reacted + benzene un reacted = 12+4=16 mol Conversion benzene = (benzene reacted/ benzene charged) x100 = (12/16) x100=75% Yield of nitrobenzene= (benzene reacted to nitrobenzene/ total benzene reacted) x 100 = (10/12) x 100= 83.33% Selectivity to nitrobenzene = (mol nitrobenzene formed /mol dinitrobenzene formed) =5/2 26. Picric acid is obtained by nitrating phenol according to the reaction C6H5OH+ 3HNO3 C6H2OH (NO2)3+3H2O. In a particular operation, 100 kg of phenol was reacted with 250 kg of HNO3 to produce 200 kg of picric acid. Which is the limiting reactant? What is the conversion of the reaction? Find the composition of the product stream by weight% and mol %. Basis: 100 Phenol C6H5OH+ 3HNO3 94 189 C6H2OH (NO2)3+3H2O 229 54 C6H5NO2 +H2O (1) = (1/1) x10= 10 mol = (1/1) x 2 = 2 mol C6H5NO2 +HNO3 C6H4 (NO2)2+H2O (2)

Mol weight of phenol= 94 , mol weight of nitric acid=63 ,molecular weight of picric acid=229, molecular weight of water=18. Weight of HNO3 required to react with 100 kg phenol= (189 /94)100= 201.06 kg HNO3 used = 250 kg. Since HNO3 used is more than the required, it is an excess reactant. Therefore phenol is the limiting reactant. 200 kg of picric acid is produced. Therefore weight of phenol reacted to give 200 kg picric acid as per stoichometry = (94/229) x 200 = 82.1 kg.

Conversion of the reaction= (limiting reactant reacted / limiting reactant taken) x100 = (82.1/100)100= 82.1 % Components leaving the reactor: Picric acid, phenol, nitric acid, water Picric acid leaving = picric acid produced = 200 kg Water leaving = water produced = (54/229)x200 = 47.16 kg Phenol leaving = phenol unreacted = phenol taken phenol reacted= 100- 82.1= 17.9 kg Nitric acid leaving = nitric acid unreacted = nitric acid taken - nitric acid reacted = 250 - (189/94) x 82.1= 250-165.07= 84.93 kg Composition of the product stream: Component Picric acid Phenol Water Nitric acid Total Weight 200.00 17.90 47.16 84.93 349.99 Weight % 57.14 5.11 13.47 24.27 99.99 Mol weight 229 94 18 63 mol 0.873 0.190 2.620 1.248 4.931 Mol% 17.70 3.85 53.13 25.31 99.99

27. Toluene reacts with nitric acid to form ortho nitro toluene and water. After carrying out the nitration operation which can be represented by the equation C6H5CH3 +HNO3 C6H4CH3NO2+H2O The product mixture was analyzed and found to contain 75% ortho nitro toluene 10% water, 15% nitric acid by weight. Comment about the conversion of the reaction. What is the % excess of the reactant used? What is the quantity of toluene used for the reaction? Basis: 100 kg of products The product does not contain toluene and therefore the conversion is 100% and also toluene is the limiting reactant. Amount of ortho nitro toluene produced= 75 kg HNO3 reacted to produce 75 kg o nitro toluene= (63/137) x 75 = 34.49 kg HNO3 unreacted= 15 kg HNO3 fed= HNO3 reacted+HNO3 unreacted= 34.49+15= 49.49 kg % excess HNO3= (15/ 34.49) x100= 43.49%

Toluene fed for the reaction= (92/ 137) x75= 50.36 kg. 28.Benzoic acid is nitrated to obtain nitro benzoic acid according to the reaction C6H5COOH+HNO3 122 63 C6H4 (COOH) NO2 + H2O. 167 18

Calculate the weight of 90% HNO3 required for reacting with 250 kg benzoic acid. If 50% excess acid is used and if the conversion is 85% find the composition of the products leaving the reactor. Basis: 250 kg benzoic acid 90% HNO3 required to react with 250 kg benzoic acid = (63/122) x250 x 100/90 =143.44 Acid used = 143.44 x 1.5 = 215.16 kg 100% acid = 215.16 x 0.9 = 193.64 kg Water entering with acid = 215.16 x 0.1= 21.52kg Conversion is 85% Benzoic acid reacted = 250 x 0.85 = 212.5 kg Benzoic acid unreacted = 250 x 0.15 = 37.5 kg HNO3 reacted = (63/122) x 212.5 = 109.73 kg HNO3 unreacted = 193.64-109.73 = 83.91 kg Water leaving = 21.52 kg Nitrobenzoic acid produced= (267/122) x 212.5= 465.06 kg Water produced= (18/122) x 212.5 = 31.35 kg Water leaving= water produced +water in acid = 31.35+21.52 = 52.87 kg Composition of the products leaving the reactor:

Component Benzoic acid Nitric acid Nitro benzoic acid Water Total

Weight 37.50 83.91 465.06 52.87 639.34

Weight% 5.87 13.12 72.74 8.27 100.00

29. Chlorobenzene is nitrated using a mixture of nitric acid and sulphuric acid. During the pilot plant studies, a charge of 100 kg chlorobenzene 106.5 kg 65.5% (by weight) nitric acid and 108.0 kg 93.6% (by weight) sulphuric acid. After two hours of operation, the final mixture was analysed.It was found that the final product contained 2% unreacted chlorobenzene. Also the product distribution was found to be 66% p nitro chloro benzene and 34% O nitro chloro benzene. Calculate a) The analysis of charge b)The % conversion of chloro benzene and c)The composition of product mixture. BASIS: 100 kg Chloro benzene The charge consists of chloro benzene and mixed acid HNO3 charged = 106.5 x 0.655 = 69.758 kg H2SO4 charged = 108.8x 0.936 = 101.088 kg Water in the charge = 106.5 x 0.345 + 108.0 x 0.064 = 43.655 kg The analysis of the reactant can be tabulated as shown Component Chloro benzene Nitric acid Sulphuric acid Water The reaction taking place are Cl Cl NO2 + + HNO3 Chloro benzene nitric acid O nitro chloro benzene water H2O mol weight 112.5 63.0 98.0 18.0 Qty Charged 100.00 69.76 101.09 43.66 314.51 Weight.% 31.80 22.18 32.14 13.88 100 .00

Cl

Cl + + HNO3 NO2 H2O

Chloro benzene nitric acid

P nitro chloro benzene

water

As given in the problem, the yield of P NCB is 66%. Since the total charge (weight) remains constant. Unreacted C.B in the product = 314.5 x 0.02 = 6.29 kg. Amount of C.B that has reacted = 100 6.29 = 93.71 kg. Conversion of C.B = 93.71 x 100 = 93.71% 100 Sulphuric acid remains unreacted From reaction I it is clear that 1 kmol of C.B 1 kg mol HNO3 1 kg mol NCB 1 kg mol H2O 112.5 kg of CB 63 kg of HNO3 Thus 63 kg of HNO3 will be consumed for converting 112.5 kg C.B into NCB Total HNO3 consumed = (63/112.5) x 93.71 =52.478 kg Unreacted HNO3 = 69.758-52.478 =17.28 kg Mol wt of NCB=157.5 Total NCB produced = (157.5/112.5) x 93.71=131.194 kg p-NCB = 0.66x131.194=86.588 KG o-NCB = 0.34x131.194 =44.606 kg Water produced = (15/112.5)x 93.71 =14.994 kg Total water produced =43.665+14.994=58.649 kg

Final product analysis: Component Weight Weight%

CB P NCB O NCB HNO3 H2SO4 H2O TOTAL

6.27 86.59 44.61 17.28 101.09 58.65 314.48

2.00 27.33 14.18 5.49 32.15 18.65 100.00

30. Acetylene is produced according to the following reaction: CaC2+2H2O C2H2+ Ca(OH)2 If 100 lit of gas is burnt per hour at 298 K (25 C) and 98.68 kpa pressure, calculate the amount of CaC2 in kg which must be used in the acetylene lamp, at the above temperature and pressure, to get 15 hours service of the lamp. CaC2 reacts to give acetylene gas to burn in the lam. Basis: 15 h of operation. Gas burning rate of acetylene= 100 lit/ hr Acetylene gas burned= 100x15= 1500 lit C2H2 generated=C2H2 burned=1500 lit

31.Ethyl alcohol is produced industrially by fermentation of molasses. The molasses sample contains 45% by weight fermentable sugar in the form of sucrose. The reactions taking lace in the fermenter are.

Sucrose

(d-Glucose) (d-Fructose)

(Monosaccharide) ton of molasses. Basis: 1000 kg of molasses.

Alcohol

Calculate the theoretical production of rectified spirit of density (0.785 kg/l) in liters per

Sucrose

(d-Glucose)

(d-Fructose)

Sucrose in molasses = 0.45 X 1000 = 450 kg From the reactions, we have

32.100 kmol of ethyl acetate is charged and hydrolyzed to produce ethyl alcohol and acetic acid. The product stream is fond to contain 45 kmol ethyl alcohol. What is the conversion? What will be the amount of acetic acid produced? Basis: 100 kmol ethyl acetate CH3COOC2H5 + H2O 88 Kmol ethyl alcohol produced= 45 kmol As per Stoichiometry 1kmol ethyl acetate gives 1 kmol ethyl alcohol Therefore kmol ethyl acetate reacted = (1/1) x 45 = 45 kmol Conversion of ethyl acetate= (ethyl acetate reacted / ethyl acetate taken) x100 = (45/100) x 100=45% Acetic acid produced / 45 kmol ethyl acetate = (1/1) x 45 = 45 kmol 33. Acetyl chloride is hydrolyzed for the production of acetic acid and hydrochloric acid. The product stream is found to contain 38.46 mol% acetic acid, 38.46% hydrochloric acid and the remaining water. Find the ratio of acetyl chloride to water used for reaction. Basis: 100 kmol products CH3COCl + H2O kmol acetic acid produced = 38.46 kmol As epr Stoichiometry 1 kmol acetic acid will be produced from 1 kmol acetyl chloride Therefore actyl chloride reacted = (1/1) x 38.46 = 38.46 kmol Water reacted= (1/1) x 38.46 = 38.46 kmol Water present in product = 100- 38.46-38.46 = 23.08 kmol = water unreacted Water fed = water reacted + water unreacted = 38.46+23.08 = 61.54 kmol Ratio of acetyl chloride to water in feed = 38.46 / 61.54 = 0.625 Neutralization 34.100 kg hydrochloric acid is neutralized by 150 kg of sodium hydroxide. What is the quantity of sodium chloride that will be produced? Find the composition of neutralized mixture by eight and mol. Basis: 100 kg HCl and 150 kg NaOH HCl+ NaOH 36.5 40 NaCl + H2O 58.5 18 CH3COOH + HCl 18 C2H5OH +CH3COOH 46 60

NaOH required to react with 100 kg HCl= (40/36.5) x 100 = 109.59 kg NaOH taken= 150 kg Since NaOH is taken more than the required, it is excess reactant As per Stoichiometry 58.5 kg sodium chloride is produced for 36.5 kg HCl Therefore sodium chloride produced= (58.5/36.5) x 100 =160.27 kg Components leaving NaCl,H2O,NaOH Water leaving=Water produced = (18/36.5) x 100 = 49.59 kg NaOH leaving = NaOH entering- NaOH reacted = 150-109.59 = 40.41 kg Sodium chloride leaving = sodium chloride produce = 160.27 kg Composition of neutralized mixture Component NaCl NaOH H2O Total weight 160.27 40.41 49.32 250 Weight % 64.11 16.16 19.73 100.00 Mol wt 58.5 40 18 mol 2.74 1.01 2.74 6.49 Mol% 42.22 15.56 42.22 100.00

35. Ammonium hydroxide is used for neutralizing acetic acid according to the reaction. CH3COOH +NH4OH CH3COONH4 +H2O If 120 kg of acetic acid is to be neutralized what will be the quantity of ammonium hydroxide required? If 25% excess NH4OH is used and if the reaction is 90% complete, what will be the composition of the product streams? Basis: 120 kg acetic acid fed CH3COOH + NH4OH 60 35 CH3COONH4 +H2O 77 18

As per Stoichiometry 35 kg NH4OH s required for 60 kg acetic acid Therefore NH4OH required to react with 120 kg acetic acid = (35/60) x 120 =70 kg NH4OH supplied = 70 x 1.25 = 87.5 kg Reaction is 90% complete Acetic acid reacted = 120 x 0.9 = 108 kg Acetic acid unreacted = acetic acid taken- acetic acid reacted = 120-108 = 12 kg

Ammonium hydroxide reacted = (35/60) x 108 = 63 kg Ammonium hydroxide unreacted = ammonium hydroxide supplied- reacted = 87.5-63 = 24.5 kg Ammonium acetate produced = (77/60) x 108 = 32.4 kg Composition of products Component Ammonium acetate Water Ammonium hydroxide Acetic Acid Total Weight 138.6 32.4 24.5 12.0 207.5 Weight % 66.80 15.61 11.81 5.78 100.00

Esterifcation 36.Ethyl acetate ester is produced by the reaction between acetic acid and ethanol using catalyst. The reaction goes to completion. The acetic acid used contained 10% water. Calculate the quantity of ethyl acetate produced for 200 kg ethanol and complete analysis of products. Basis: 200 kg ethanol CH3COOH+ C2H5OH 60 46 CH3COOC2H5 +H2O 88 18

As per Stoichiometry 88 kg ethyl acetate produced for 46 kg ethanol Therefore ethyl acetate produced for 200 kg ethanol= (88/46) x 200 = 382.61 kg 46 kg ethanol requires 60 kg acetic acid Therefore 200 kg ethanol requires = (60/46) x 200 = 260.87 kg Acetic acid used is 90% pure 90% acetic acid used = 260.87x100/90 = 289.86 kg Water in acetic acid = 189.86 - 260.87 = 28.99 kg Water produced= (18/46) x 200 = 78.26 kg Water leaving= water produced+ water with acid = 78.26 + 28.99 = 107.25 kg

Complete analysis of products Component Ethyl acetate Water Total Weight 382.61 107.25 489.86 Weight% 78.11 21.89 100.00

37. In the manufacture of ethyl benzoate, benzoic acid is reacted

with ethanol in

presence of catalyst. The feed mixture is taken in a batch reactor along with catalyst and at the end of reaction the products were analyzed and found to contain 35% ethyl benzoate, 35% water, 10% ether and 20% benzoic acid. What is the % conversion of the reaction? Which is the excess reactant and what is the % excess? Basis: 100 kmol reaction products C6H5 COOH+ C2H5OH Benzoic acid ethanol Ethyl benzoate in products = 35 kmol As per Stoichiometry 1 kmol ethyl benzoate requires I kmol benzoic acid and 1 kmol ethanol Therefore kmol benzoic acid reacted = (1/1) x 35 = 35 kmol Kmol ethanol reacted= (1/1) x 35 = 35 kmol Kmol benzoic acid fed = benzoic acid reacted + benzoic acid unreacted = 35+20= 55 kmol Kmol ethanol fed = kmol ethanol reacted + kmol ethanol unreacted = 35+10= 45 kmol Since benzoic acid fed is more than the required to react with ethanol, benzoic acid is excess reactant and ethanol is the limiting reactant Conversion= (ethanol reacted/ ethanol fed) x100 = (35/45) x 100 = 77.78% % excess benzoic acid = [(benzoic acid fed- benzoic acid required) / benzoic acid required] x 100 = [(55-45)/45] x 100 = (10/45) x 100 = 22.22% C6H5COOC2H5+ H2O ethyl benzoate

Neutralization 38.100 kg hydrochloric acid is neutralized by 150 kg of sodium hydroxide. What is the quantity of sodium chloride that will be produced? Find the composition of neutralized mixture by eight and mol. Basis: 100 kg HCl and 150 kg NaOH HCl+ NaOH 36.5 NaOH taken= 150 kg Since NaOH is taken more than the required, it is excess reactant As per Stoichiometry 58.5 kg sodium chloride is produced for 36.5 kg HCl Therefore sodium chloride produced= (58.5/36.5) x 100 =160.27 kg Components leaving NaCl,H2O,NaOH Water leaving=Water produced = (18/36.5) x 100 = 49.59 kg NaOH leaving = NaOH entering- NaOH reacted = 150-109.59 = 40.41 kg Sodium chloride leaving = sodium chloride produce = 160.27 kg Composition of neutralized mixture Component NaCl NaOH H2O Total weight 160.27 40.41 49.32 250 Weight % 64.11 16.16 19.73 100.00 Mol wt 58.5 40 18 mol 2.74 1.01 2.74 6.49 Mol% 42.22 15.56 42.22 100.00 40 NaCl + H2O 58.5 18

NaOH required to react with 100 kg HCl= (40/36.5) x 100 = 109.59 kg

39. Ammonium hydroxide is used for neutralizing acetic acid according to the reaction. CH3COOH +NH4OH CH3COONH4 +H2O If 120 kg of acetic acid is to be neutralized what will be the quantity of ammonium hydroxide required? If 25% excess NH4OH is used and if the reaction is 90% complete, what will be the composition of the product streams?

Basis: 120 kg acetic acid fed CH3COOH + NH4OH 60 35 CH3COONH4 +H2O 77 18

As per Stoichiometry 35 kg NH4OH s required for 60 kg acetic acid Therefore NH4OH required to react with 120 kg acetic acid = (35/60) x 120 =70 kg NH4OH supplied = 70 x 1.25 = 87.5 kg Reaction is 90% complete Acetic acid reacted = 120 x 0.9 = 108 kg Acetic acid unreacted = acetic acid taken- acetic acid reacted = 120-108 = 12 kg Ammonium hydroxide reacted = (35/60) x 108 = 63 kg Ammonium hydroxide unreacted = ammonium hydroxide supplied- reacted = 87.5-63 = 24.5 kg Ammonium acetate produced = (77/60) x 108 = 32.4 kg Composition of products Component Ammonium acetate Water Ammonium hydroxide Acetic Acid Total Weight 138.6 32.4 24.5 12.0 207.5 Weight % 66.80 15.61 11.81 5.78 100.00

Esterifcation 40.Ethyl acetate ester is produced by the reaction between acetic acid and ethanol using catalyst. The reaction goes to completion. The acetic acid used contained 10% water. Calculate the quantity of ethyl acetate produced for 200 kg ethanol and complete analysis of products. Basis: 200 kg ethanol CH3COOH+ C2H5OH 60 46 CH3COOC2H5 +H2O 88 18

As per Stoichiometry 88 kg ethyl acetate produced for 46 kg ethanol Therefore ethyl acetate produced for 200 kg ethanol= (88/46) x 200 = 382.61 kg

46 kg ethanol requires 60 kg acetic acid Therefore 200 kg ethanol requires = (60/46) x 200 = 260.87 kg Acetic acid used is 90% pure 90% acetic acid used = 260.87x100/90 = 289.86 kg Water in acetic acid = 189.86 - 260.87 = 28.99 kg Water produced= (18/46) x 200 = 78.26 kg Water leaving= water produced+ water with acid = 78.26 + 28.99 = 107.25 kg Complete analysis of products Component Ethyl acetate Water Total Weight 382.61 107.25 489.86 Weight% 78.11 21.89 100.00

41. In the manufacture of ethyl benzoate, benzoic acid is reacted

with ethanol in

presence of catalyst. The feed mixture is taken in a batch reactor along with catalyst and at the end of reaction the products were analyzed and found to contain 35% ethyl benzoate, 35% water, 10% ether and 20% benzoic acid. What is the % conversion of the reaction? Which is the excess reactant and what is the % excess? Basis: 100 kmol reaction products C6H5 COOH+ C2H5OH C6H5COOC2H5+ H2O Benzoic acid ethanol ethyl benzoate Ethyl benzoate in products = 35 kmol As per Stoichiometry 1 kmol ethyl benzoate requires I kmol benzoic acid and 1 kmol ethanol Therefore kmol benzoic acid reacted = (1/1) x 35 = 35 kmol Kmol ethanol reacted= (1/1) x 35 = 35 kmol Kmol benzoic acid fed = benzoic acid reacted + benzoic acid unreacted = 35+20= 55 kmol Kmol ethanol fed = kmol ethanol reacted + kmol ethanol unreacted = 35+10= 45 kmol Since benzoic acid fed is more than the required to react with ethanol, benzoic acid is excess reactant and ethanol is the limiting reactant

Conversion= (ethanol reacted/ ethanol fed) x100 = (35/45) x 100 = 77.78% % excess benzoic acid = [(benzoic acid fed- benzoic acid required) / benzoic acid required] x 100 = [(55-45)/45] x 100 = (10/45) x 100 = 22.22% Alkylation 42. Ethyl benzene is manufactured by the action of benzene with ethyl chloride using anhydrous aluminium chloride as catalyst.The reaction is C6H6 Benzene + ClC2H5 ethyl chloride C6H5C2H5 + ethyl benzene HCl

Ethyl chloride is used 15% in excess of theoretically required. The reaction is 95% complete. During alkylation the liberated HCl is scrubbed with water in order to obtain 20%HCl solution by weight. Calculate the raw materials required for 3000 kg of ethyl benzene produced and the amount of 20% HCl produced. Basis: 1 kmol benzene C6H6 + C2H5Cl 78 64.5 C6H5C2H5 + HCl 106 36.5

As per stoichometry I kmol benzene requires 1 kmol ethyl chloride Ethyl chloride required= (1/1) x 1 = 1 kmol Ethyl chloride fed= 1x1.15 = 1.15 kmol Weight of ethyl chloride fed= 1.15 x 64.5= 74.175 kg Reaction is 95% complete Therefore ethyl benzene produced = (1/1) x 1 x 0.95 = 0.95 kmol Weight of ethyl benzene produced = 0.95 x 106 = 100.7 kg HCl produced = (1/1) x 1 x 0.95 = 0.95 kmol Weight of HCl produced = 0.95 x 36.5 = 34.675 kg Benzene unreacted = 1-0.95 = 0.05 kmol = 0.05 x 78 = 3.9 kg To produce 20% solution of HCl, water required = (80/20) x 34.675 = 138.7 kg Total weight of HCl produced = 138.7+ 34.675 = 173.375 kg Benzene required for 3000 kg ethyl benzene = (78/100.7) x 3000 = 2323.73 kg Ethyl chloride fed for 3000 kg ethyl benzene = (74.175/100.7) x 3000 = 2209.78 kg

43. One method of producing toluene is by alkylation of benzene by chloromethane using aluminium chloride catalyst. In a particular operation 200 kg of benzene and 150 kg of chloro methane are used to produce 200 kg of toluene. The HCl produced is absorbed using 200 kg water to obtain HCl solution. Calculate a) the % excess chloromethane used b)the composition of raw materials entering c)the degree of completion of reaction and d) concentration of HCl solution produced by completely absorbing the HCl gas produced. Basis: 200 kg benzene and 150 kg chloromethane fed C6H6+ CH3Cl 78 50.5 C6H5CH3 +HCl 92 36.5

Chloromethane required to react with 200 kg benzene = (50.5/78) x 200 = 129.49 kg % excess chloromethane used = [(150-129.49) / 129.49] x 100 = 15.84% Composition of raw material entering Component Benzene Chloromethane Total Weight 200 150 350 Weight % 57.14 42.86 100.00

Toluene produced = 200 kg Benzene reacted to produce 200 kg toluene = (78/92) x 200 = 169.57 kg Conversion of benzene= (benzene reacted/benzene fed) x 100 = (169.57/200) x 100 = 84.785% HCl produced = (36.5/92) x 200 = 79.35 kg Water used for absorption= 200 g Total HCl solution produced = 200 + 79.35 = 279.35 kg Concentration of HCl solution = (79.35/279.35) x 100 = 28.41% AMINATION 44. The reaction between acetone and ammonia to form amino propane is carried out in a batch reactor. The final products stream is analyzed and found to contain 35 mol% amino propane, 35 mol% water 20 mol% ammonia and the remaining acetone. The

feed to the reactor contains only acetone and ammonia. Calculate the fractional conversion of the limiting reactant and the % by which the other reactant is in excess. Basis: 100 kmol of products formed CH3COCH3+ NH3 Acetone CH3-CH-NH2-CH3+H2O Amino propane

The products contain 20 mol% NH3 and 10% acetone As per Stoichiometry the requirement of acetone and ammonia are same, but the product stream contains 20% unreacted NH3 and 10% unreacted acetone Therefore NH3 is the excess reactant and acetone is limiting reactant Mole amino propane in product = 35 kmol Therefore acetone reacted = (1/1) x 35 = 35 kmol Acetone fed= acetone reacted+ acetone unreacted = 35 +10 = 45 kmol % conversion= (35/45) x 100 = 77.78% NH3 reacted= (1/1) x 35 = 35 kmol NH3 fed = NH3 reacted + NH3 unreacted = 35 + 20 = 55 kmol Ammonia required to react with 45 kmol acetone = (1/1) x 45 = 45 kmol % excess NH3 fed = [(55-45)/45] x 100 = (10/45) x 100 = 22.22% 45. Calculate the composition of products obtained by amination of benzyl chloride with 60% excess NH3.Assume the reaction proceeds according to the reaction C6H5COCl+NH3 Benzyl chloride The conversion is 90%. Basis: 1 kmol benzyl chloride C6H5COCl+NH3 NH3 required= (1/1) x 1 = 1 kmol NH3 fed= 1x1.6= 1.6 kmol Conversion is 90% Kmol benzyl chloride leaving = benzyl chloride unreacted = 1 x (1-0.9) = 0.1 kmol Ammonia leaving = ammonia unreacted = ammonia fed- ammonia reacted =1.6- (1/1) x 0.9 = 0.7 kmol C6H5CONH2+HCl C6H5CONH2+HCl Benzmide

Benzamide leaving = benzamide produced = (1/1) x 0.9 = 0.9 kmol HCl leaving = HCl produced = (1/1) x 0.9 = 0.9 kmol Composition of products Component Benzamide Hydrochloric acid Benzyl chloride Ammonia Total Mol 0.9 0.9 0.1 0.7 2.6 mol % 34.62 34.62 3.85 26.92 100.01