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Kevin Dunn, kevin.dunn@mcmaster.ca Due date: 21 January 2013 Assignment objectives: math refresher; chemistry refresher; review mol balances Always state assumptions in this assignment, midterms and exams. Never use an equation by just writing it down; state its origin and all simplifying assumptions. For example: using the general mol balance in a batch reactor, under the assumption of a well-mixed and dNj constant volume system, we have: = rj V dt

Question 1 [10]

1. 2. 3. 4.

1 dx = x 1 dx = x2 1 dx = ax + b 1 dx = x

5. When do we require an integration constant; and when do we not require it? Solution 1. 2. 3. 4. 1 dx = ln x + C x 1 1 dx = + C 2 x x 1 1 dx = ln(ax + b) + C ax + b a 1 dx = 2 x + C x

5. We require an integration constant when the limits of integration are unspecied (indenite integrals); otherwise we dont require the constant, since the integral is uniquely dened.

Question 2 [10]

1. A vessel contains a gas of concentration 20 mol.m3 . The gas is stored at 375C. Assuming this is an ideal gas, what is the pressure in the vessel measured in kPa? What assumption are you making (apart from the ideal-gas law)?

2. A constant volume batch reactor operates at 14.7 psi and 1340F. The reactor volume is 290 ft3 . How many mols are in the system, assuming an ideal gas? Solution Assumptions: Pure species in tank, at constant volume and temperature. 1. T = 648 K, so from the ideal gas law: P = CRT = (20 mol.m3 )(8.314 J.mol1 .K 1 )(648 K) = 107.7 kPa. 2. At P = 14.7 psi = 1 atm, with V = 290 ft3 = 8.205 m3 and T = 1000 K, then R = 8.205746 105 m3 .atm.K1 .mol1 , giving n = 100 mol.

Question 3 [10]

Milk is pasteurized if it is heated to 63C for 30 min, but if it is heated to 74C it only needs 15 seconds for the same result. Find the activation energy of this sterilization process. Recall the activation energy for a chemical reaction is the E term, and the rate constant in is given by E k = k0 e RT . Hint: assume pasteurization proceeds via rst-order kinetics; what is the reactant? Solution To ask for the activation energy of a process means assuming an Arrhenius temperature dependency for the process. Here we are told that t1 = 1800 seconds are required at temperature T1 = 336 K t2 = 15 seconds are required at temperature T2 = 347 K As told, assuming rst order kinetics, rA = kA CA = k0 e RT CA . For a batch system, making the regular assumption of constant volume and well-mixed (both are suitable for pasteurization):

CA

E

t=

CA0

dCA = rA

CA CA0

dCA 1 = ln kA CA kA

CA CA 0

So for the 2 systems we have that CA0 and CA are the same, so we can write the ratio:

E

kA,2 t1 1800 k0 e RT2 = = 120 = = E t2 15 kA,1 k0 e RT1 Simplifying, recognizing that k0 , and R are the same for both systems: E E + RT2 RT1 E 1 1 ln(120) = R 347 336 ln(120)(8.314) E = 9.43 105 E = 421885 J.mol1 120 = exp

Question 4 [13]

The fermentation of an active ingredient A is to be carried out in a reactor. The reaction kinetics are given by: A R rA = 0.1CA mol 1 + 0.5CA L.min

1. Consider a batch reactor lled with 750 L of reactant at CA,0 = 2 mol.L1 . How long must the reactor be operated to achieve an exit concentration of A of 0.1 mol.L1 ? If the feed rate is continuously fed at 25 L.min1 , with CA,0 = 2 mol.L1 . Determine the volume required for a 2. CSTR 3. PFR to achieve an exit concentration of A of 0.1 mol.L1 . 4. Which of the CSTR or PFR require a smaller volume? Solution 1. For a well-mixed batch reactor, the design equation is: dCA = rA dt

CA

C A0

dt

t=0

10 ln

0.1 2.0

2. Using the design equation for CSTRs (assuming it to be well-mixed and operating at steady state, with a constant volumetric ow rate of 25 L.min1 ): V = = FA0 FA rA 50 2.5

(0.1)(0.1) 1+(0.5)(0.1)

= 4987.5 5000 m3 3. Use the mole balance equation for PFRs, making the usual assumption of steady state, and wellmixed in the radial direction, and using that (q )(dCA ) = dFA , assuming constant volumetric ow

throughout the PFR: dFA = rA dV dCA dV = q rA 1.0 + 0.5CA dCA 0.1CA CA0 0.1 V = (25)(10) ln (25)(5)(0.1 2.0) 2.0 V = 986 L V =q

Question 5 [7]

CA

The gas phase reaction: A B + C is carried out at 100C in a 20 L constant-volume, sealed batch reactor, at atmospheric pressure. The reaction 2 where k = 2 L.mol1 .min1 . is second order: rA = kCA One mole of pure A is initially placed in the reactor, which is well mixed (is this a reasonable assumption?). Determine: 1. the partial pressure due to A in the reactor 2. the concentration of A in the reactor after 5 minutes have elapsed 3. the partial pressure due to A in the reactor after 5 minutes have elapsed. Solution There was an error in the question, so as long as you attempted the question you got full grade. The problem was over-specied, so you get a partial pressure of A that exceeds atmospheric pressure. 1. pa V = nA RT , or solving for pA = (1)(8.314)(373) = 155056 Pa. 20 103 2. After 5 minutes in a batch reactor that is assumed to be well-mixed: dNA = rA V dt dCA = rA dt

t CA

dt =

t=0 C A0

t=

1 kA

dCA 2 kCA 1 1 CA CA 0

CA = 0.033 mol.L1

3. The partial pressure due to A after 5 minutes have elapsed is pA = CA RT = (33.0)(8.314)(373) = 102337 Pa 4

Question 6 [10]

Consider a municipal water treatment plant for a smallish community. Waste water at 32, 000 m3 .day1 , ows through the treatment plant with a mean residence time of 8 hours. Air is bubbled through the tanks, and microbes in the tank attack and break down the organic material: CO2 + H2 O Organic waste + O2 A typical entering feed has a BOD (biological oxygen demand) of 200 (mg O2 ).L1 , the efuent has a negligible BOD. Find the average rate of reaction, or decrease in BOD, in the treatment tanks. Solution The rate of reaction is dened as rO2 = mol O2 used . (day)(m3 ) V or that V = q

microbes

We can obtain an estimate of the tank volume from the residence time equation: =

32000 = 10667 m3 . 3 To obtain a value for the numerator, recognize that 1 mole of waste requires 1 mole of oxygen to remove 0.2 g.L1 its biological oxygen demand. We require 200 mg of oxygen though per litre of waste, or 32 g.mol1 1000 L.m3 = 6.25 mol of oxygen required per m3 of waste. There will be 32000 m3 .day1 of waste water mol O2 used 6.25 32000 = 18.75 . to treat, so this corresponds then to an average reaction rate of 10667 (day)(m3 ) END

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