1. A hydrocarbon is burnt with excess air. The Orsat analysis of the flue gas shows 10.81% CO2, 3.

78% O2 and 85.40 N2. Calculate the atomic ratio of C:H in the hydrocarbon and the % excess air. Calculations: 100 moles of dry flue gas (i.e., excepting H2O) The Orsat analysis shows the compositions of the flue gases by not taking into account of H2O. From the composition of air(mole %), Here, nitrogen is the tie component. 79 mole of N2 h 21 mole of O2 Therefore, O2 that is entering the burner = 85.4 x 21/79 = 22.7 C + O2 CO2 1 mole of CO2 h 1 mole of O2 h 1 atom of C ( i.e.,1 mole of O2 reacts with 1 atom of C to produce 1 mole of CO2) Therefore, O2 used up for reacting with carbon = 10.81 mole and, Carbon in the hydrocarbon = 10.81 atoms O2 reacted with Hydrogen in the hydrocarbon = 22.7 - (10.81 + 3.78) = 8.11 4H + O2 2H2O 1 mole of O2 reacts with 4 atoms of hydrogen. Therefore, hydrogen in the hydrocarbon = 8.11 x 4 = 32.44 atoms. C:H ratio in the hydrocarbon = 1 : 32.44/10.81 = 1 : 3 Theoretical air demand = air needed for complete conversion of carbon to carbon dioxide and hydrogen to water vapor % excess air = 100 x (actual air used - theoretical air demand) / theoretical air demand = 100 x (22.7 - (10.81 + 8.11))/( 10.81 + 8.11) = 20%

2. Natural gas containing 80% CH4, 15% C2H6 and 5% C3H8 is burnt with 50% excess air. Assuming that 90% of the carbon in the hydrocarbons are converted to CO2 and the rest to CO, determine Flue gas analysis Orsat analysis Calculations: Basis: 1 mole of natural gas Component CH4 0.80 C2H6 0.15 C3H8 0.05 Total 1.0 Reactions: C + O2 CO2 C + 1/2 O2 CO H + 1/4 O2 1/2 H2O Mole Atoms of C Atoms of H 0.8 x 1 = 0.8 0.8 x 4 = 3.2 0.15 x 2 = 0.3 0.15 x 6 = 0.9 0.05 x 3 = 0.15 0.05 x 8 = 0.4 1.25 4.5

-- I -- II -- III

90% of Carbon is converted by reaction I, and 10% of carbon is converted by II. Amount of CO2 produced = 1.25 x 0.9 = 1.125 mole Amount of CO produced = 1.25 x 0.1 = 0.125 mole

Amount of H2O produced = 4.5 / 2 = 2.25 mole Amount of O2 used by hydrocarbon = O2 used by reactions I, II and III. = 1.125 + 0.125 x (1/2) + 4.5 x (1/4) = 2.3125 mole Theoretical O2 needed = Oxygen for complete conversion of C to CO2 and H to H2O. = 1.25 + 4.5 x (1/4) = 2.375 mole Oxygen entering = 150% of theoretical = 1.5 x 2.375 = 3.5625 mole Therefore, nitrogen entering = 3.5625 x 79/21 = 13.4018 mole = N2 in the flue gas O2 in the flue gases = O2 entering - O2 used = 3.5625 - 2.3125 = 1.25 mole Flue gas analysis: Component Moles Mole % CO2 1.125 6.20 CO 0.125 0.69 H2O 2.25 12.39 O2 1.25 6.89 N2 13.4018 73.83 Total 18.1518 100 Orsat analysis (Water free): Component Moles Mole % CO2 1.125 7.07 CO 0.125 0.79 O2 1.25 7.86 N2 13.4018 84.28 Total 15.9018 100 Balance of Individual Reactions: Basis: 1 mole of Natural gas CH4 0.80 C2H6 0.15 C3H8 0.05 Total 1.0 CH4 + 2 O2 CO2 + 2 H2O CH4 + 3/2 O2 CO + 2 H2O

-- 1 -- 2 -- 3

C2H6 + 7/2 O2 2 CO2 + 3 H2O C2H6 + 5/2 O2 2 CO + 3 H2O -- 4 C3H8 + 5 O2 3 CO2 + 4 H2O -- 5 C3H8 + 7/2 O2 3 CO + 4 H2O -- 6

In the above reactions CO2 is produced from reactions 1, 3 and 5. Since 90% of Carbon is converted to CO2 and 10% to CO, CO2 produced = (1 x 0.8 + 2 x 0.15 + 3 x 0.05) x 0.9 = 1.125 mole Similarly CO is obtained from reactions 2, 4 and 6. CO produced = (1 x 0.8 + 2 x 0.15 + 3 x 0.05) x 0.1 = 0.125 mole H2O produced = (2 x 0.8 + 3 x 0.15 + 4 x 0.05) x 0.9 + (2 x 0.8 + 3 x 0.15 + 4 x 0.05) x 0.1 = 2.25 mole O2 used up in these reactions = (2 x 0.8 + 3.5 x 0.15 + 5 x 0.05) x 0.9 + (1.5 x 0.8 + 2.5 x 0.15 + 3.5 x 0.05) x 0.1 = 2.3125 mole

Theoretical O2 needed = moles of O2 needed for Conversion of C to CO2 and H to H2O. = 2 x 0.8 + 3.5 x 0.15 + 5 x 0.05 = 2.375 mole O2 entering = 50 % excess = 150% of theoretical = 2.375 x 1.5 = 3.5625 mole N2 entering along with O2 in the air = 3.5625 x 79/21 = 13.4018 mole (sine air is 21% O2 and 79% N2 by volume). O2 in the flue gas = O2 entering - O2 used up = 3.5625 - 2.3125 = 1.25 mole N2 in the flue gas = N2 entering = 13.4018 mole Therefore, for 1 mole of Natural gas entering, the flue gas coming out are: Component Moles CO2 1.125 CO 0.125 H2O 2.25 O2 1.25 N2 13.4018 Total 18.1518 On comparing with the data obtained from atomic balance and balance of individual reactions, it can be seen that the results are same from either method. But instead of lengthy calculations for individual reactions, we can very well make use of atomic balances. 3. Air at 30oC and 150 kPa in a closed container is compressed and cooled. It is found that the first droplet of water condenses at 200 kPa and 15oC. Calculate the percent relative humidity of the original air. The vapor pressures of water at 15oC and 30oC are 1.7051 kPa and 4.246 kPa respectively. Calculations: At 15oC, and 200 kPa water is at 100% humidity. i.e., Percentage humidity or percentage absolute humidity = 100 x [pA(p - pS)]/[ pS(p - pA)] = 100 Therefore, pA/(p - pA) = pS/(p - pS) where pA = partial pressure of water vapor; pS = vapor pressure of water vapor p = total pressure of system i.e., no of moles of water vapor per mole of dry air = 1.7051/(200 - 1.7051) = 0.0086 This ratio (moles of water vapor / mole of dry air) is not going to change for a closed system. Therefore, partial pressure of A at 30oC and 150 kPa is found as follows: pA/(p - pA) = 0.0086 pA/(150 - pA) = 0.0086 pA + 0.0086 pA = 1.29 pA = 1.29/1.0086 = 1.279 kPa Percentage relative humidity of the original air: percentage relative humidity = 100 x (pA/pS) = 100 x 1.279/4.246 = 30.12% 4. Nitrogen from a cylinder is bubbled through acetone at 1.1 bar and 323 K at the rate of 2 x 10-4 m3/min. The nitrogen, saturated with acetone vapor leaves at 1.013 bar, 308 K at the rate of 3.83 x 10-4 m3/min. What is the vapor pressure of acetone at 308 K? Calculations: Using Ideal gas law, molal flow rate of nitrogen is calculated as follows:

Molal density of nitrogen rm = n/V = P/RT = 1.1 x 105/(8314 x 323) = 0.04096 kmol/m3 Therefore, molal flow rate = 2 x 10-4 x 0.04096 = 8.1934 x 10-6 kmol/min Similarly the molal density of leaving gases = 1.013 x 105/(8314 x 308) = 0.03956 kmol/m3 and the molal flow rate of leaving gases = 3.83 x 10-4 x 0.03956 = 1.5151 x 10-5 kmol/min Since the molal rate of nitrogen is not going to change, molal flow rate of acetone in the leaving gases = 1.5151 x 10-5 - 8.1934 x 10-6 = 6.9578 x 10-6 kmol/min Mole fraction of acetone in the leaving gases = 6.9578 x 10-6 / 1.5151 x 10-5 = 0.4592 And partial pressure of acetone in the leaving gases = 0.4592 x 1.013 = 0.4652 Bar At saturation conditions, partial pressure of vapor is equal to its vapor pressure. Therefore, vapor pressure of acetone at 308 K = 0.4652 Bar. 5. An evaporator is fed continuously with 25 kg/hr of a solution which contains 10% NaCl, 10% NaOH and 80% H2O. During evaporation, H2O is removed from the solution and NaCl precipitates as crystals which is settled and removed. The concentrated liquor leaving the evaporator contains 50% NaOH, 2% NaCl and 48% H2O. Calculate (i)Weight of salt precipitated per hour. (6) (ii) Weight of concentrated liquor leaving per hour. (6) Calculations: Data: Flow rate of feed = 25 kg/hr Composition of feed (F): NaCl 10% NaOH 10% H2O 80% Composition of concentrated liquor (P): NaCl 2% NaOH 48% H2O 50% Balance for NaOH: NaOH entering the in feed = NaOH leaving in concentrated liquor i.e., 0.1 x 25 = 0.50 P Therefore, the mass flow rate of concentrated liquor (P) = 0.1 x 25 / 0.50 = 5 kg/hr Balance for NaCl: NaCl entering in the feed = 25 x 0.1 = 2.5 kg/hr The entering NaCl is coming out as crystals and in the concentrated liquor. NaCl leaving in the concentrated liquor = 0.02 P = 0.02 x 5 = 0.1 kg/hr Therefore, NaCl precipitated = 2.5 - 0.1 = 2.4 kg/hr

6. A solution of ethyl alcohol containing 8.6% alcohol by weight is fed at the rate of 5000 kg/hr to a continuous fractionating column operating at atmospheric pressure. The distillate which is the desired product contains 95.4% alcohol by weight and the residue from the bottom of the column contains 0.1% alcohol by weight. Calculate the following: i. the mass flow rates of the distillate and residue in kg/hr, and ii. the percentage loss of alcohol. Calculations:

Overall material balance: Feed = Distillate + Residue i.e., F = D + R D + R = 5000 1 Component balance for Alcohol: FxF = DxD + RxR Where x 's are the mole fraction of alcohol in various streams. 0.954 D + 0.001 R = 5000 x 0.086 = 430 2 Equations 1 and 2 contains 2 unknowns D and R, and that can be solved as follows: Multiplying equation 1 by 0.001, 0.001D + 0.001 R = 5 3 subtracting equation 3 from equation 2, 0.953 D = 425 D = 446 kg/hr i.e., Distillate flow rate = 446 kg/hr Therefore, R = 5000 - 446 = 4554 kg/hr i.e., Residue flow rate = 4554 kg/hr Ethanol leaving in the residue (i.e., ethanol lost) = 4554 x 0.001 = 4.554 kg/hr Ethanol entering in the feed = 5000 x 0.086 = 430 kg/hr Percentage loss of ethanol = 100 x (4.554 / 430) = 1.06
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7. 220 kg of CO2 gas at 27 C and 1 atm is compressed adiabatically to 1/5th of its volume. It is then cooled to its original temperature at constant volume. Find Q, DU and W for each step and for the entire process. Formula: For an ideal gas, PV = nRT g For an adiabatic process, PV = constant, (1/ V2/V1 = (P1/P2) g ) ( T2/T1 = (V1/V2) g -1) Adiabatic work of compression, W = (P2V2 - P1V1) / (g - 1) 1 Q + W = DU DU = mCV(T2 - T1) 2 Calculations: Here there are two steps taking place. 1. Adiabatic compression, and 2. Constant volume heat removal. n = 220 / Molecular weight of CO2 = 220/44 = 5 kmol 5 3 V1 = 5 x 8314 x (273 + 27) / (1.01325 x 10 ) = 123.08 m . 3 V2 = (1/5) x 123.08 = 24.616 m . g = 1.3 (for CO2: data) 0.3 T2 = 300 x (5) = 486.2 K P1/P2 = (V2/V1)g g P2 = 1 / (1/5) i.e., P2 = 8.103 atm. Adiabatic compression work W can be calculated from equn.1 or equn.2 (since DU = Q + W; and Q = 0 for an adiabatic process). 5 5 W = (8.103 x 1.01325 x 10 x 24.616 - 1.01325 x 10 x 123.08) / 0.3 = 25.7985 MJ Since the temperature of the system is returned to its original state, the internal energy change of the total process is zero. Therefore, DU for the heat removal step is = -25.7985 MJ. For the constant volume cooling step, W = 0, and DU = -25.7985 MJ. Therefore, Q for this step = 25.7985 MJ. Summary:

Q Step 1 0 Step 2 -25.7985 MJ Over all

W 25.7985 MJ 0

DU 25.7985 MJ -25.7985 MJ

-25.7985 MJ (heat removed from the 25.7985 MJ (work added to the 0 system) system)

8. A vertical cylinder with a freely floating piston contains 0.1 kg air at 1.2 bar and a small electric resistor. The resistor is wired to an external 12 Volt battery. When a current of 1.5 3 Amps is passed through the resistor for 90 sec, the piston sweeps a volume of 0.01 m . Assume (i) piston and the cylinder are insulated and (ii) air behaves as an ideal gas with Cv = 700 J/(kg.K). Find the rise in temperature of air. Calculations: Energy added by electric resistor = V I t = 12 x 1.5 x 90 = 1620 J 5 5 Work done = - PdV = -P(V2 - V1) = -1.2 x 10 x DV = 1.2 x 10 x 0.01 = 1200 J DU = Q + W = 1620 - 1200 = 420 J (energy added to the system and work added to the system are taken as positive.) DU = mCVDT DT = 420/(0.1 x 700) = 6 K.
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9. A 28 liter rigid enclosure contains air at 140 kPa and 20 C. Heat is added to the container until the pressure reaches 345 kPa. Calculate the heat added. Formulae: For an ideal gas, PV = nRT From first law of thermodynamics, Q + W = DU For an ideal gas DU is a function of temperature only, and work done at constant volume = 0 Therefore, Q = DU. And, DU = mCV(T2 - T1) m = n x Molecular weight Calculations: -3 n = PV / (RT) = 140 x 1000 x 0.028 / (8314 x 293) = 1.609 x 10 kmol -3 m = 1.609 x 10 x 29 = 0.0467 kg. For constant volume system, P a T. Therefore, P1/T1 = P2/T2 140/293 = 345/T2 T2 = 722 K. o o CV = 0.718 kJ/kg. C (data, for air at 20 C) Q = DU = 0.0467 x 0.718 x (722 - 293) = 14.385 kJ i.e., Heat added = 14.385 kJ

10. A thermodynamic system undergoes a cycle composed of a series of three processes for which Q1 = +10 kJ, Q2 = +30 kJ, Q3 = -5 kJ. For the first process, DE = +20 kJ, and for the third process, DE = -20 kJ. What is the work in the second process, and the net work output of the cycle? Calculations: Q + W = DE Work done in the first process = 20 - 10 = 10 kJ (i.e., work is done on the system) Work done in the third process = -20 - (-5) = -15 kJ For a cyclic process, the overall internal energy change is zero. (i.e., DE = 0) Therefore, DE in the second process = (0 - (20 - 20)) = 0 kJ

Therefore, work done in the second process = 0 - 30 kJ = -30 kJ. Total work done during the cycle = 10 + (-15) + (-30) = -35 kJ (i.e., 35 kJ of work is done by the system). Total work done can also be calculated as follows: Total Q = Q1 + Q2 + Q3 = 10 + 30 - 5 = 35 kJ Therefore, net work done during the cycle = 0 - 35 kJ = -35 kJ (the negative sign indicates that work is done by the system). 11. Air is compressed from 2 atm absolute and 28 C to 6 atm absolute and 28 C by heating at constant volume followed by cooling at constant pressure. Calculate the heat and work requirements and DE and DH of the air. Calculations: PV = nRT We have to rise the pressure to 6 atm by heating at constant volume. At constant volume, P a T. Therefore, T2/T1 = P2/P1 T2 = (6/2) x (273 +28) = 903 K For a constant volume process, W = 0 and DE = Q o CV = 0.718 kJ/kg. C (for air; data) Q = mCV(T2 - T1) = 0.718 x (903 - 301) = 432.24 kJ/kg. DE = 432.24 kJ/kg For cooling at constant pressure, heat removed = mCP(T2 - T1) = 1.005 x (903 - 301) = 605.01 kJ/kg (Cp - Cv = R for ideal gas) Internal energy change for the total process consisting the above two steps is zero (since internal energy is a function of temperature alone). Work done on the gas during constant pressure cooling = 605.01 - 432.24 = 172.77 kJ/kg. Summary: Heat required Work required DE Constant Volume heat addition 432.24 kJ/kg 432.24 kJ/kg DH 605.01 kJ/kg
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Constant Pressure heat removal -605.01 kJ/kg 172.77 kJ/kg Over All -172.77 kJ/kg 172.77 kJ/kg

-432.24 kJ/kg -605.01 kJ/kg 0 0

12. A tank having a volume of 0.1 m contains air at 14 MPa and 50 C. It is connected through 3 a valve to a larger tank having a volume of 15 m , which is completely evacuated. The entire assembly is completely insulated. The valve is opened and the gas allowed to come to equilibrium in both tanks. Calculate the final pressure. Calculations: For this process, Q = 0 and W = 0. Therefore, DU = 0. DU = mCvDT = 0. Therefore, DT = 0. For an ideal gas, PV = nRT Since T is constant, P1V1 = P2V2 14 x 0.1 = P2 x (0.1 + 15) i.e., final pressure P2 = 92.715 KPa. 13. Liquid water at 25 C flows in a straight horizontal pipe, in which there is no exchange of either heat or work with the surroundings. Its velocity is 12 m/s in a pipe with an i.d. of 2.5 cm until it flows into a section where the pipe diameter increases to 7.5 cm. What is the temperature change? Calculations: For the steady flow process, the first law is written as
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DH + Du /2 + gDz = Q + W s since there is no shaft work, W s = 0 and flow is horizontal, Dz = 0 Therefore, 2 DH + Du /2 = Q and since there is no heat transfer, Q = 0 2 Therefore, DH + Du /2 = 0 Applying continuity equations, u1A1r1 = u2A2r2 for water r1 = r2 Therefore, 2 2 2 2 u2/u1 = A1/A2 = d1 /d2 = 2.5 /7.5 = 0.1111 u2 = 12 x 0.1111 = 1.333 m/s 2 2 2 2 (u2 - u1 ) / 2 = (1.333 - 12 ) / 2 = -71.11 Therefore, DH = 71.11 J/kg Enthalpy change per kg mass = 71.11 J o We know, DH = mCpDT and, m = 1000 g; Cp = 4.184 J/g. C Therefore, o DT = 71.11/(1000 x 4.184) = 0.017 C o Temperature change = 0.017 C 14. An existing process consists of two steps: (a) One mole of air T1 = 900 K and P1 = 3 bar is cooled at constant volume to T 2 = 300 K. (b) The air is then heated at constant pressure until its temperature reaches 900 K. It is proposed to replace this two-step process by a single isothermal expansion of the air from 900 K and 3 bar to some final pressure P. What is the value of P that makes the work of the proposed process equal to that of the existing process? Assume mechanical reversibility and treat air as an ideal gas with Cp = 7R/2 and Cv = 5R/2 Calculations: Work in the original process consisting of two steps: (a) For the constant volume process: W=0 Pressure at the end of the constant volume process (P2): P1V1 = RT1 V1 = R x 900 / 3 = 300R P2V2 = RT2 Since V1 = V2, P2 = R x 300 / (300R) = 1 bar (b) For the constant pressure process: P2 = 1 bar; T2 = 300 K; V2 = 300R P3 = 1 bar; T3 = 900 K P3V3 = RT3 V3 = R x 900 / 1 = 900R W = PdV = P2(V3 - V2) = 1 x (900R - 300R) = 600R Total work done in the two step process = 600R For the single step isothermal process: W = 600R = RT ln (P1/P) i.e., 600R = R x 900 x ln (3/P) ln(3/P2) = 600/900 = 2/3 (2/3) e = 3/P 1.9477 = 3/P P = 3/1.9477 = 1.54 bar 15. One kilogram of air is heated reversibly at constant pressure from an initial state of 300 K and 1 bar until its volume triples. Calculate W, Q, DU, and DH for the process. Assume air 3 -1 -1 -1 -1 obeys the relation PV/T = 83.14 bar cm mol K and that Cp = 29 J mol K .

Calculations: 3 -1 -1 From the relation, PV/T = 83.14 bar cm mol K 3 Initial molal volume = 83.14 x 300 /1 = 24942 cm /mol 3 = 24.942 m /kmol 3 3 i.e. Initial volume of 1 kg of air (V1) = 24.942 m / 29 = 0.86 m 3 6 3 Final volume (V2)= 3 x V1 = 3 x 0.86 = 2.58 m = 2.58 x 10 cm . 3 Final specific volume = 24942 x 3 = 74826 cm /mol Final temperature: P2 x 74826 = T2 x 83.14 1 x 74826 = T2 x 83.14 T2 = 900 K For the constant pressure heating process, 6 6 3 5 W = -P(V2 - V1) = -1 x (2.58 x 10 - 0.86 x 10 ) bar cm = -1 x 10 x (2.58 - 0.86) Nm = -172000 J = -172 kJ. (work is done by the system by expansion) Moles of air in 1 kg mass = 1000/29 = 34.483 mol Q = mCpDT = 34.483 x 29 x (900 - 300) = 600000 J = 600 kJ. DU = Q + W = 600 - 172 = 428 kJ (heat given to the system and work done on the system are positive quantities) DH = Q = 600 kJ Summary: W -172 kJ Q 600 kJ DU 428 kJ DH 600 kJ 16. Liquid water at 100 C and 1 bar has an internal energy (on an arbitrary scale) of 419 kJ/kg 3 and a specific volume of 1.044 cm /g. (a) What is its enthalpy? o (b) The water is brought to the vapor state at 200 C and 800 kPa, where its enthalpy is 2838.6 3 kJ/kg and its specific volume is 260.79 cm /g. Calculate DU and DH for the process. Calculations: (a) Enthalpy = U + PV -3 3 = 419 + 100 kPa x 1.044 x 10 m /kg = 419 + 0.1044 = 419.1044 kJ/kg o (b)Internal energy of water vapor at 200 C and 800 kPa = H - PV -3 = 2838.6 - PV = 2838.6 - 800 x 260.79 x 10 = 2838.6 - 208.632 = 2629.968 kJ/kg DU = 2629.968 - 419 = 2211.968 kJ/kg DH = 2838.6 - 419.1044 = 2419.4956 kJ/kg
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17. The decomposition of NO2 follows a second order rate equation. Data at different temperatures are as follows: T (K) 592 603 627 651.5 656 3 k (cm /gmol.sec) 522 755 1700 4020 5030 Compute the energy of activation Energy from the data. The reaction is 2NO 2 2NO + O2 Calculations: Activation energy is found from the Arrhenius' relation -E/RT k = ko e i.e., ln k vs. 1/T is a straight line with a slope of -E/R where, E is the activation energy; and R is the universal gas constant. T (K) 592 603 627 651.5 656 k (cm /gmol.sec)
3

522

755

1700

4020

5030

1/T ( K ) ln k

-1

0.001689 6.257668

0.001658 6.626718

0.001595 7.438384

0.001535 8.299037

0.001524 8.523175

From the above data, the following graph is drawn, and the slope is = -13622 Therefore, E/R = 13622 E = 13622 x 8314 = 113253.3 kJ/kmol
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18. The thermal decomposition of nitrous oxide (N 2O) in the gas phase at 1030 K is studied in a constant volume vessel at various initial pressures of N 2O. The half-life data so obtained are as follows: po (mm Hg) t1/2 (sec) 52.5 860 139 470 290 255 360 212

2N2O 2N2 + O2 Determine the rate equation that fits the data. Calculations: t1/2 Vs. CAO in a log-log plot is a straight line with a slope of 1-n CAo = pAo/RT = po/RT (for an ideal gas) ln(CAo) Vs. ln(t1/2) in a linear XY plot gives a straight line, and the slope of the line is 1 - n from the above figure, 1-n = -0.7469 therefore, n = 1 + 0.7469 = 1.7469 = 1.75 i.e., Order of the reaction (n) = 1.75 t1/2 and CAo are related by the formula:

for a value of po = 290, and t1/2 = 255, -5 -3 CAo = (290/760) x 1.01325 x 10 /(8314 x 1030) = 4.515 x 10 gmol/lit. therefore, 1.75 - 1 -3 (1-1.75) -1 -0.75 k = (2 - 1) x (4.515 x 10 ) / (255 x (1.75 - 1)) = 0.2046 sec .(gmol/lit) the rate expression for the given reaction is, 1.75 -rN2O = 0.2046 (C N2O) 19. Establish the kinetics of the thermal decomposition of Nitrous oxide from the following o data and find the reaction rate at 990 C and an initial pressure of 200 mm Hg. t, min 20 53 100

% decomposition 23 50 73 Calculations: Conversion (XA)of Nitrous oxide (A) for various time values are given are given. We shall test the date for first order, second order kinetics by integral method of analysis. For a first order reaction, -ln(1 - XA) vs. t is a straight line. t, min 20 53 100 XA 0.23 0.50 0.73

t, min XA 1-XA -LN(1 - XA)

20 0.23 0.77 0.261365

53 0.5 0.5 0.693147

100 0.73 0.27 1.309333

From the above data the following graph is drawn:

For a second order reaction, XA/(CAo (1- XA) ) = kt i.e., XA/(1 - XA) vs. t is a straight line t, min 20 53 XA/(1 - XA) 0.298701 1

100 2.703704

From the above data the following graph is drawn: By comparing the two graphs, it can be seen that First order kinetics is well fiiting the given data. Fisrt -1 order rate constant k is obtained from the slope of the first order data graph, and it is = 0.0131 sec . Therefore, -rA = kCA = kCAo(1 - XA) = kpAo(1 - XA)/RT = (1 - XA) x 0.0131 x (200/760) x 101325 /(8314 x -5 (990 + 273)) = 3.327 x 10 (1 - XA) -5 i.e., -rA = 3.327 x 10 (1 - XA) where XA is fractional decomposition of Nitrous oxide, and -rA is the rate of decomposition of Nitrous oxide.

20. The gas phase decomposition of A takes place according to the irreversible reaction, A 3P. The kinetics of the reaction was studied by measuring the increase in pressure in a o constant volume reaction vessel. At 504 C and an initial pressure of 312 mm Hg, the following data were obtained: Time (Sec) Total pressure (mm Hg) 390 408 777 488 1195 562 3155 779 a 931

a. Test for a first order reaction. o b. Calculate the value of the specific reaction rate at 504 C Calculations: Total pressure of the system (p) and partial pressure of A (pA)are related as: pA = pAo - (a/Dn)(p - po) where, po is the initial pressure of the system; pAo is the initial pressure of A; a is the stoichiometric coefficient of A; and Dn = stoichiometric coefficient of products minus reactants. For the given problem, po = pAo = 312 mm Hg (Assuming feed is pure A) a=1 Dn = 3-1 = 2 pA = 312 - (1/2)(p - 312) i.e., pA = 312 - 0.5 (p - 312) pA for various times are calculated as follows: Time (Sec) 390 777 1195 3155 a Total pressure (mm Hg) 408 488 562 779 931 pA (mm Hg) 264 224 187 78.5 2.5 Fractional conversion of A is given by: XA = (pAo - pA) / pAo For various time values, XA and -ln(1- XA) is calculated and tabulated as follows:

Time (Sec) 390 777 1195 3155 a pA (mm Hg) 264 224 187 78.5 2.5 XA 0.154 0.282 0.401 0.748 0.992 -ln(1 - XA) 0.167 0.331 0.512 1.378 4.828 For a first order reaction, a plot of t Vs. -ln(1 - XA) in a linear XY graph is a straight line with a slope of k. From the following plot, it is seen that the given data is for a first order reaction. 21. Acetic acid is hydrolysed in three stirred tank reactors operated in series. The feed flows 3 to the first reactor (V = 1 lit) at a rate of 400 cm /min. The second and third reactors have volumes of 2 and 1.5 litres respectively. The first order irreversible rate constant is 0.158 -1 min . Calculate the fraction hydrolysed in the effluent from the third reactor. Calculations: The design equation for series, steady flow mixed reactor is Vi =FAo (XA,i - XA,i-1) / (-rA)i Where Vi = volume of reactor i FAo = molal flow rate of A into the first reactor XA,i = fractional conversion of A in the reactor i XA,i-1 = fractional conversion of A in the reactor i-1 For first order reaction, -rA,i = kCA,i = kCAo(1 - XA,i) 3 v = volumetric flow rate of A = 400 cm /min = 0.4 lit/min For the first reactor: (V = 1 lit) (-rA)1 = (kCA)1 = k CA,1 = k CAo ( 1- XA,1) CAo= FAo / v i.e., FAo = v CAo XA,i-1 = XA,0 = 0 Therefore, Vi =FAo (XA,i - XA,i-1) / (-rA)i 1 = 0.4 (XA,1 - 0) / (0.158 x ( 1 - XA,1 ) ) XA,1 = 0.283 For the second reactor: (V = 2 lit) (-rA)2 = (kCA)2 = k CA,2 = k CAo ( 1- XA,2) Therefore, (-rA)2 = k CAo ( 1- XA,2) XA,1 = 0.283 FAo = v CAo Vi =FAo (XA,i - XA,i-1) / (-rA)i 2 = 0.4 (XA,2 - 0.283) / ( k ( 1- XA,2) ) 5 k = (XA,2 - 0.283) / ( 1- XA,2) 0.79 - 0.79 XA,2 = XA,2 - 0.283 1.073 = 1.79 XA,2 XA,2 = 0.60 For the third reactor: (V = 1.5 lit) (-rA)3= (kCA)3 = k CA,3 = k CAo ( 1- XA,3) XA,2 = 0.6 FAo = v CAo Vi =FAo (XA,i - XA,i-1) / (-rA)i 1.5 = 0.4 (XA,3 - 0.60) / ( k ( 1- XA,3) ) 0.5925 = (XA,3 - 0.60) / ( 1- XA,3) 0.5925 - 0.5925 XA,3 = XA,3 - 0.60 1.1925 = 1.5925 XA,3 XA,3 = 0.749 The fraction hydrolyzed in the effluent from the third reactor = 0.749 22. The decomposition of phosphine is irreversible and first order at 650 C. 4PH3(g) P4(g) + 6H2(g) -1 The rate constant (sec ) is reported as
o

log k = (-18993/T ) + 2 log T + 12.13 (log to the base 10) o where T is in K. In a closed vessel (constant volume) initially containing phosphine at 1 atm pressure, what will be the o pressure after 50, 100 and 500 sec. The temperature is maintained at 650 C. Calculations: Total pressure of the system (p) and partial pressure of A (pA)are related as: pA = pAo - (a/Dn)(p - po) If phosphine is taken as A, then pAo = po = 1 atm a = stoichiometric coefficient of A = 4 Dn = stoichiometric coefficient of products - stoichiometric coefficient of reactants =1+6-4=3 Therefore, pA = 1 - 4/3 (p - 1), 4/3 (p - 1) = 1 - pA i.e., p = 0.75 (1 - pA) + 1 o Rate constant k, at 650 C (= 650 + 273 = 923 K)is found from the relationship for k and T log k = (-18993/T ) + 2 log T + 12.13 log k = -18993/923 + 2 log 923 + 12.13 log k = -2.517 -2.517 k = 10 -3 -1 Therefore, k = 3.04 x 10 sec . For the first order equation, -ln (CA/CAo) = k t or -ln (pA/pAo) = kt -kt pA/pAo = e -kt -3 -3 pA = pAo e = 1 x exp(-3.04 x 10 t) = exp(-3.04 x 10 t) for various time values, pA is calculated and tabulated as follows: t, sec 50 100 500 pA, atm 0.860 0.738 0.219 From the relationship of total pressure(p) and partial pressure of A (pA), p = 0.75 (1 - pA) + 1 total pressure for various time values are calculated as: t, sec 50 100 500 pA, atm 0.860 0.738 0.219 p, atm 1.105 1.197 1.586

23. The kinetics of an aqueous phase decomposition of A is investigated in two CSTR's in series, the first having half the volume of the second. At steady state with a feed concentration of 4 gmol/lit., and mean residence time of 65 sec in the second reactor, the concentration of feed to second from the first is found to be 2 gmol/lit., while that of the stream leaving the second is 1 gmol/lit. Find the suitable kinetic rate expression. Calculations: Data: Residence time of second reactor = 65 sec t1 = V1/v = (C0 - C1)/ (-r)1 t2 = V2/v = (C1 - C2)/ (-r)2 Conversions based on the feed to the reactors = 50% = 0.5 (4 to 2 gmol/lit in first reactor, and 2 to 1 gmol/lit in second reactor) st Test for 1 order: for first order reaction, -rA = k CAo(1 - XA) and where, CAo = concentration of A in the feed to the reactor; and XA = fractional conversion of A in the reactor

for the second reactor (-r)2 = k 2 x 0.5 = k since t2 = 65 sec, and C1 - C2 = 2 - 1 = 1 gmol/lit i.e., 65 = 1/k 1 for the first reactor, V1= V2/2 and t1 = 65/2 = 32.5 sec. for the first reactor (-r)1 = k 4 x 0.5 = 2k i.e., 32.5 = (4 - 2)/2k = 1/k 2 st from equn.1 and 2 it is seen that 1 order mechanism is not suitable. nd Test for 2 order: nd 2 2 for 2 order reaction, -rA = k CAo (1 - XA) and 2 2 for the second reactor (-r)2 = k x 2 x 0.5 = k t2 = V2/v = (C1 - C2)/ (-r)2 i.e., 65 = (2 - 1)/k = 1/k 65 = 1/k 3 2 2 for the first reactor (-r)1 = k x 4 x 0.5 = 4k t1 = V1/v = (C0 - C1)/ (-r)1 32.5 = (4 - 2)/4k = 1/2k i.e., 65 = 1/k 4 On comparing equn.3 and 4 it could be seen that the given data is for a second order reaction. k = 1/65 lit/(gmol.sec) = 0.0154 lit/(gmol.sec) 2 and, -rA = 0.0154 CA gmol/(lit.sec) 24. Water at 20 C (viscosity = 1 cp) flows through a smooth straight pipe A of inside diameter 4 cm at an average velocity of 50 cm/sec. Oil flows through another pipe B of inside diameter 10 cm. Assuming similarities, calculate the velocity of oil through pipe B. Specific gravity of oil is 0.8 and its viscosity is 2 cp. Data: A: Dia of A = 4 cm Velocity of fluid in A = 50 cm/sec Density of fluid in A = 1 g/cc Viscosity of fluid in A = 1 cp B: Dia of B = 10 cm Density of fluid in B = 0.8 g/cc Viscosity of fluid in A = 2 cp Formulae: For dynamic similarity, ratio of forces to be equal Inertial forceA / Inertial forceB = Viscous forceA / Viscous forceB i.e. NReA = NReB Calculations: NReA = NReB Therefore, 4 x 50 x 1 / 1 = 10 x VB x 0.8 / 2 200 = 4 VB VB = 200/4 = 50 cm/sec Velocity of oil through B = 50 cm/sec 25. A geometrically similar model of an air duct is built 1:30 scale and tested with water which is 50 times more viscous and 800 times more dense than air. When tested under dynamically similar conditions, the pressure drop is 2.25 atm in the model. Find the corresponding pressure drop in the full-scale prototype. Data:
o

Dimensions of the model = 1/30 times the dimensions of prototype Viscosity of fluid in the model = 50 times the viscosity of fluid in prototype Density of fluid in the model = 800 times the density of the fluid in prototype Formulae: For dynamic similarity, ratio of forces to be equal Inertial forcem / Inertial forcep = Pressure forcem / Pressure focep = Viscous forcem / Viscous forcep 1 2 2 Pressure force = (2frLv / D)D (i.e. = frictional pressure drop x area) 2 From 1, NRem = NRep Calculations: NRem = NRep 1 x vm x 800 / 50 = 30 x vp x 1 / 1 vm = 1.875 vp 2 2 2 2 Pressure force ratio = (2fm x 800 x 1 x vm / 1) x 1 / ((2fp x 1 x 30 x (vm / 1.875) / 30) x 30 ) 2 2 = 1600fmvm / 512fpvm =3.125fm/fp -0.25 f = 0.079 (Dvr/m) -0.25 -0.25 -0.25 -0.25 fm/fp = (1 x vm x 800 / 50) / (30 x (vm/1.875) x 1 / 1) = 16 /16 =1 2 2 pressure ratio = 3.125 x 30 / 1 = 2812.5 ( i.e. pressure = pressure force/area) 2 Pressure drop of the prototype = 2.25/2812.5 atm = 0.0008 atm = 81.06 N/m 26. A U-tube manometer filled with mercury is connected between two points in a pipeline. If the manometer reading is 26 mm of Hg, calculate the pressure difference between the o points when (a) water is flowing through the pipe (b) air at atmospheric pressure and 20 C is flowing in the pipe. Density of mercury = 13.6 gm/cc Density of water = 1 gm/cc Molecular weight of air = 28.8 Data: Manometer reading(h) = 26 mm Hg = 0.026 m Hg Density of mercury(rm) = 13.6 gm/cc Density of water = 1 gm/cc Molecular weight of air(MW) = 28.8 o Temperature of air = 20 C = 293 K R = 8314 J/(kmol.K) Formulae: For simple U - tube manometer, P1 - P2 = Dp = (rm - r)gh. Ideal Gas law PV = n RT Molal density = n/V = P/(RT) Mass density(r) = Molecular weight x molal density Calculations: (a) Water is flowing through the pipe: 2 Dp = (rm - r)gh = (13600 - 1000) x 9.812 x 0.026 = 3214.4 N/m o (b) Air at atmospheric pressure and 20 C is flowing in the pipe: 3 r = 28.8 x 101325/(8314 x 293) = 1.2 kg/m 2 Dp = (rm - r)gh = (13600 - 1.2) x 9.812 x 0.026 = 3469.2 N/m 27. 2.16 m /h water at 320 K is pumped through a 40 mm I.D. pipe through a length of 150 m in a horizontal direction and up through a vertical height of 12 m. In the pipe there are fittings equivalent to 260 pipe diameters. What power must be supplied to the pump if it is 60% efficient? Take the value of fanning friction factor as 0.008. Water viscosity is 0.65 cp, and density = 1 gm/cc. Data: 3 3 3 Flow rate(Q) = 2.16 m /h = 2.16/3600 m /sec = 0.0006 m /sec Dia of pipe(D) = 40 mm = 0.04 m
3

Length of pipe in horizontal direction = 150 m Length of pipe in vertical direction(Dz) = 12 m Equivalent length of fittings = 260 pipe diameters Friction factor(f) = 0.008 Efficiency of pump(h ) = 0.6 Viscosity of fluid(m) = 0.65 cp = 0.00065 kg/(m.sec) 3 Density of fluid(r) = 1 gm/cc = 1000 kg/m Formulae: 1. Bernoulli's equation

2. Frictional losses per unit mass of flowing fluid

3. Power required for pumping = (mass flow rate x head developed by pump)/ h = (volumetric flow rate x pressure developed by pump)/ h Calculations: Length of pipe with fittings = 150 + 12 + 260 x 0.04 m = 172.4 m Velocity = volumetric flow rate/flow cross sectional area 2 = 0.0006/((p/4) x 0.04 ) = 0.477 m/sec 2 2 2 hf = 2 x 0.008 x 172.4 x 0.477 / 0.04 = 15.69 m /sec frictional losses per unit weight of fluid(h) = hf / g = 15.69/9.812 = 1.6 m pump head(q) = Dz + h = 12 + 1.6 = 13.6 m 2 pressure developed by pump = 13.6 x 1000 x 9.812 = 133443.2 N/m power required for pumping = 0.0006 x 133443.2 / 0.6 = 133.4 watt = 133.4/736 HP = 0.181 HP

28. Brine of specific gravity 1.2 is flowing through a 10 cm I.D. pipeline at a maximum flow rate of 1200 liters/min. A sharp edged orifice connected to a simple U-tube mercury manometer is to be installed for the purpose of measurements. The maximum reading of the manometer is limited to 40 cm. Assuming the orifice coefficient to be 0.62, calculate the size of the orifice required. Data: 3 3 Density of brine (r) = 1.2 x 1000 kg/m = 1200 kg/m Dia of pipe (Da) = 10 cm = 0.1 m 3 3 Maximum flow rate (Q) = 1200 liters/min = 1.2 m /min = 0.02 m /sec Maximum manometer reading (hm) = 40 cm = 0.4 m of Hg 3 Density of manometric fluid (rm) = 13600 kg/m Orifice coefficient (Co) = 0.62 Formulae: Velocity at the orifice

Where b = Db/Da Db = dia of orifice Da = dia of pipe For the U-tube manometer, Pa - Pb = (rm - r)ghm Calculations: 2 Pa - Pb = (13600 - 1200) x 9.812 x 0.4 = 48667.5 N/m

The quantity (1 - b ) will be approximately 1. Therefore, 0.5 Vb = 0.62 x ( 2 x 48667.5 / 1200 ) = 5.584 m/sec 2 Cross sectional area of orifice = volumetric flow rate / velocity at the orifice = 0.02 / 5.584 = 0.00358 m 0.5 Dia of orifice (Db) = (0.00358 x 4/p) = 0.0675 m = 6.75 cm 29. A Newtonian fluid having a viscosity of 1.23 poise, and a density of 0.893 gm/cm , is flowing through a straight, circular pipe having an inside diameter of 5 cm. A pitot tube is installed on the pipeline with its impact tube located at the center of the pipe cross section. At a certain flow rate, the pitot tube indicates a reading of 8 cm of mercury. Determine the volumetric flow rate of the fluid. Data: Viscosity of fluid (m) = 1.23 poise = 0.123 kg/(m.sec) 3 3 Density of fluid (r) = 0.893 gm/cm = 893 kg/m Dia of pipe (D) = 5 cm = 0.05 m Manometer reading (hm) = 8 cm of Hg = 0.08 m of Hg Formulae: Velocity at the center of pipe 0.5 0.5 Vo = ( 2 x (Ps - Po ) / r ) = ( 2 x hm x (rm - r) x g / r ) Calculations: 0.5 Vo = ( 2 x 0.08 x (13.6 - 0.893) x 9.812 / 0.893 ) = 4.73 m/sec NRe = D x Vo x r / m = 0.05 x 4.73 x 893 / 0.123 = 1717 Since the flow is laminar (NRe < 2100), the average velocity is given by Vavg = Vo / 2 = 4.73 / 2 = 2.365 m/sec (velocity at the centerline is the maximum velocity) 2 2 3 Volumetric flow rate = Vavg x p x D / 4 = 2.365 x p x 0.05 / 4 = 0.00464 m /sec = 4.64 lit/sec 30. A rotameter calibrated for metering has a scale ranging from 0.014 m /min to 0.14 m /min. 3 It is intended to use this meter for metering a gas of density 1.3 kg/m with in a flow range 3 3 of 0.028 m /min to 0.28 m /min. What should be the density of the new float if the original 3 one has a density of 1900 kg/m ? Both the floats can be assumed to have the same volume and shape. Data: Old: 3 Density of float (rf)= 1900 kg/m 3 Density of gas (r) = 1.3 kg/m 3 Qmin = 0.014 m /min New: 3 Density of gas (r) = 1.3 kg/m 3 Qmin = 0.028 m /min Formula:
3 3 3

Where Q = volumetric flow rate A2 = area of annulus (area between the pipe and the float) A1 = area of pipe Af = area of float Vf = volume of float CD = rotameter coefficient Calculations: From the equation, for the same float area and float volume and the pipe geometry, 0.5 Q = k (rf - r) where k is a proportionality constant 0.5 Qnew / Qold = ( (rfnew - r) / (rfold - r) )

i.e. 0.028 / 0 .014 = ( (rfnew - 1.3) / (1900 - 1.3) ) 0.5 2 = (rfnew - 1.3) / 43.574 0.5 (rfnew - 1.3) = 87.15 (rfnew - 1.3) = 7595.1 3 rfnew = 7596 kg/m

0.5