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v 0.08, last updated March 17, 2006

This document is a collection of manuals of Chemical Engineering-related experiments that have been oered at various times in the past few years. The Undergraduate Laboratory course structure has been modied, and as a result, students will now perform 40 experiments over 4 semesters. In the interim period before the new course structure is ratied, these experiments will run under the existing course/credit structure. Several new experiments are due to be phased in, to better integrate concepts from dierent courses. In addition to descriptions of the various experiments, this manual contains (i) discussion of relevant aspects of Safety that students are expected to observe during their experimentation, and (ii) basic principles of data analysis that are expected to be followed in presenting their results. Course-specic details (including the evaluation procedure followed and the rotation schedule) may be obtained on the UG lab webpage http://www.che.iitb.ac.in/courses/uglab/uglabs.html UG Lab Coordinators

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Contents

1 MS207: Determination of Apparent Porosity 2 MS401: Residence Time Distribution 3 MS402: Continuous Reactive Distillation 4 MS403: Verication of Debye-Huckel Theory 5 MS404: Ion Exchange Columns 6 MS405: Gas-Liquid and Liquid-Liquid Reaction 7 MS406: High Performance Thin Layer Chromatography 4 9 14 20 27 32 37

8 MS407: Metal Recovery from a Dilute Solution by an Electrochemical Method 40 9 MS408: Electrosynthesis of Manganese (III) Acetate in a Packed Bed Reactor 45 10 MT301: Hydrodynamics of packed columns 11 MT302: Dierential Distillation 12 MT303: Distillation with Total Reux 13 MT304: Gas-Liquid Absorption 14 HT301: Thermal Conductivity of Insulating Powder 15 HT302: Heat Transfer by Combined Natural Convection and Radiation 16 HT303: Boiling and Condensation Studies 48 52 56 59 62 64 66

17 HT304: Heat Transfer Through a Submerged Helical Coil in an Agitated Vessel (Under Unsteady-State Conditions) 71 18 HT305: Heat Transfer Through Coiled Tubes in an Agitated Vessel (Under Steady-State Conditions) 78 19 HT306: Heat Transfer in a Packed Bed 20 HT307: Finned Tube Heat Exchanger 21 HT208: Heat Transfer in Laminar Flow 22 HT209: Heat Transfer in Turbulent Flow 80 84 88 93

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23 FM201: Flow Through Piping Networks 24 FM202: Nature of Flow 25 FM303: Frictional Losses in Pipe Fittings and Valves 26 FM204: Viscosity Measurement 27 FM305: Agitation and Mixing 28 FM406: Two Phase Flow in Vertical Tubes

97 99 101 102 103 104

29 TH201: Determination of Partial Molar Enthalpies by Adiabatic Calorimetry 108 30 TH202: Ebulliometric Determination of Vapour Pressures 111

31 TH203: Ebulliometric Determination of the `Innite Dilution Activity Coecient' (IDAC) 113 32 TH204: Determination of the Dynamic Surface Tension of a surfactant by using Bubble Pressure Tensiometer 115 33 TH206: Vapour Liquid Equilibrium 34 BL301: Total Protein Estimation by Lowry's Method 35 BL302: Determination of pKa by pH Titration Method 36 BL303: Aseptic Culture Techniques 37 BL304: Kinetics of Alkaline Phosphatase 38 RE301: Kinetics of a (Solid-Liquid) Esterication Reaction 39 RE302: Batch Reactive Distillation 40 RE303: Micellar Catalysis 41 RE304: Homogeneous Reactions 42 RE305: Interfacial (Liquid-Liquid) Nitration A Data Analysis 118 122 124 126 128 131 136 142 146 148 151

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4 . suspended weight (S) from the saturated weight (W) and the actual volume of open pores (V1) in cubic centimeters by subtracting the dry weight (D) from the saturated weight (W). shall be weighed (S) while suspended in the immersion liquid of the same density as that in the desiccator. unless the test material is unstable in contact with it.4 shall be used. Admit the immersion liquid slowly till the specimen is covered. Reduce the pressure in the desiccator to a value not greater than 25 mm of mercury. Test Specimen . Then weigh the soaked test piece suspended in air (W).An apparatus capable of reducing the pressure to a value not greater than 25 mm of mercury. Liquid paran may be used with all types of refractory material but it shall be fractionated before use and the fraction boiling below 200◦ C shall be rejected.Test specimen measuring 65×65×40 mm shall be cut form the brick or shape as to remove the original surface of the refractory under test. • Place the test specimen after weighing in an empty vaccum desiccator. Allow the specimen to stand under reduced pressure for at least 5 to 6 hours. Test specimen .1 g.1) The Boiling Water Method General .1 Determination of Apparent Porosity The Evacuation Method General:.Test specimen as given under 9. shall be used. • Obtain the exterior volume (V) in cubic centimeters of the test specimen by subtracting the Calculation Obtain the apparent porosity (P) in percent from either of the following formulae P = V1 × 100 V P = W −D × 100 W −S (1. This weighing and all subsequent weighings shall be made to an accuracy of 0. For this purpose a cut-o grinding wheel is recommended. Care should be taken that the lter paper does not come into contact with the surface of the test piece since the removal of too much liquid will lead to large errors than the removal of insucient liquid. Any loosely adhering grog or dust shall be removed from the test piece before use.The boiling water method of the determination of apparent porosity is applicable to burnt bricks only. Procedure • Dry the test specimen at 110◦ C and weigh after cooling to room temperature in a desiccator. Air shall then be allowed to enter the vessel and the test specimen held in a sling of ne thread. Immersion Liquid:. • Lift the test piece slowly from the immersion liquid by means of a sling.The evacuation method of the determination of apparent porosity is applicable to all types of refractories. Evacuating Apparatus:.1. The sides of a test piece will drain during this operation and the globules of liquid that form on the under-sided and between the sling and the top surface shall be removed by brief contact with the edge of a piece of lter paper.Water may be used.

During boiling. Place the test specimen in distilled water and boil for two hours. It is not applicable to materials attacked by water. After boiling and cooling.Procedure 1. 4.1 g. and then allow to cool to room temperature while still immersed in water. This weighing and all subsequent weighings shall be made to an accuracy of 0. Crush the pieces between hardened steel surfaces to a maximum particle size of 3 mm thoroughly mix the crushed material and reduce by quartering to a test sample of 50 g. Dry the test specimen at 110◦ C and weigh after cooling to room temperature in a desiccator. ensure that the test specimen is not in contact with the heated bottom of the container. weigh the test specimen (S) while suspended in water. Determination of true specic gravity and true density Objective This test determines the true specic gravity and true density of refractory materials under prescribed conditions.4 and calculate the apparent porosity as given in 9. 4. 2. 3. Remove by a magnet any magnetic material introduced in crushing or grinding 5 . Immediately after obtaining the suspended weight remove the test specimen from water. Take two pieces of the size of a walnut from dierent positions of a solid specimen in such a way as to exclue any part of the original exterior surface (skin). 2. Preparation of Sample 1.5.1.6. If the material submitted for testing is already crushed or ground thoroughly mix a representative portion of at least 500 g and reduce by quartering to a test sample of 50 g. blot lightly with a moistened towel and weigh in air (W). Apparatus Analytical Balance and Weights 50-ml Pycnometer Bottle with Capillary Tube Stopper Thermometer Drying Oven Weighing Bottle Desicator A suitable apparatus to produce a vaccum of 12 to 25 mm mercury pressure. 5. the exterior volume of the test specimen (V) and true volume of open pores (V1) as in 9. Grind the entire 50-g sample in an agate mortar to such a neness that it will pass through IS Sieve 15. 3. Heat the specimen in a container which does not give o scale. Do the grinding either by hand or by mechanical sample grinder so constructed as to prevent the introduction of any impurity 5.1.

P = weight in g of the stoppered pycnometer.3) 6 . Then weigh the pycnometer and contents (W2). do it in such a way as not to withdraw any water from the capillary tube. Then ll the pycnometer with distilled water at room temperature (t◦ C). Calculations Calculate the true specic gravity in accordance with the following formula: Specic gravity = W −P (W − P ) − (W1 − W2 ) (1. Dry the pycnometer and stopper at 105◦ C. stopper and sample (W). wipe o excess water from the stopper and the pycnometer thoroughly with a lintless towel.001 g. obtain them at the same temperature within the limits of 0. Note 1: Exercise caution during boiling so that it is not suciently vigorous to cause loss of the sample due to popping. cool in a desiccator. Dry the 50 g sample to constant weight at 105◦ C to 110◦ C and place in a glass stoppered weighing bottle. Place approximately 8 to 12 g of the sample in the dry pycnometer. Afte boiling.3◦ C. and W1 = weight in g of the stoppered pycnometer lled with water. Use a constant temperature bath controlled to 0.1◦ C. weigh the pycnometer. any variation in room temperature (t) when obtaining weights (W1) and (W2) will introduce an appreciable error.2) where t = temperature of the material and the water in ◦ C. Make duplicate tests on material from the 50-g sample. and avoid any selective sampling. 2. Procedure 1. The true density of the sample may be determined without additional measurement in accordance with the following formula : True Density = Specic gravity × (dw − da ) (1. insert the stopper. Then empty the pycnometer and again dry. cool to room temperature (t◦ C) in a water-bath. and again weigh (W1) with the stopper in place. If the boiling is done at atmospheric pressure. Note 2: Fill the pycnometer so that there is an overow of water through the capillary tube when the stopper is inserted. W2 = weight in g of the stoppered pycnometer. sample. and water. Record all weights to the nearest 0. weigh (p) on an analytical balance. it is advisable to insert with the stopper a thin strip of paper before the boiling operation. Fill the pycnometer to one-fourth to one half of its capacity with distilled water. Therefore. When wiping the excess water from the tip of the stopper. 3. and boil the water (See Note 1) at atmospheric or under reduced pressure for approximately 10 to 15 minutes.6. Take care in all stages of preparation of the test sample not to exclude any portions that are dicult to grind. ll the pycnometer with distilled water (See Note 2). W = weight in g of the stoppered pycnometer and sample.

Porosity is always expressed in percentage. Porosity is aected by • The nature of the material. 7 . Hence porosity of the body prepared from the material is higher. of the body in water: D Saturated wt.).where dw = density of water at the temperature at which the test was carried out.001. Note: These are however. and then the density of the liquid has to be taken into account. DIATOMACEOUS EARTH. Closed or sealed Continuous or isolated Size of pore : big. cracks. not included in the said I.g. of the body in air: W Wt. Report the determinations to the nearest 0. Absorption TYPES OF PORES Open or apparent. medium. small Distribution : Well distributed or appearing as defects such as holes. e. of the body with water: S Sealed porosity is known by nding out the density of the body (True density). Total Bulk volume = Open pore volume + closed pore volume + Volume of the material If water aects the material than other liquid is to be used.Specication i) Bulk density ii) Water absorption Porosity Porosity Eects: Density (Bulk). and da = density of air at the temperature at which the test was made. Thermal Conductivity Thermal resistance of the body Strength at room temperature as well as at high temperature Permeability Corrosion or Chemical attack Surface properties (smoothness etc. Apparent porosity (Open)% : (Open pore volume/Bulk volume)×100 Sealed porosity % : 100 × (Sealed pore volume/B Volume) True porosity %: 100 × (Total pore volume/B Volume) Open Porosity Open porosity is found out from: Wt.S. Calculate also the following from the obtained results. Certain materials have micro porosity and cannot be easily reduced. etc.

one or more of the following reasons: • Temperature of ring and time. sulphated etc. arrangement of the particles from which the body is prepared. • Amount of water used during fabrication • Physical and chemical reactions that occur when materials is red in the furnace to get the nal shape such as phase change accompanied by expansion and contraction. extru- sion and fusion etc. frothing. bloating. machine or hydraulic moulding. slip-casting. loss of water of crystallization etc..• Particle size. At higher temperatures the body reduces its porosity due to Melt formation Crystallisation or recrystallisation Diusion : Solid-solid. • Method of preparation. Hand Moulding. even less than 1 per cent. shape. • Normal refractories which have been red in the furnace to get the nal shape have 10 to 30 per cent porosity • Insulating refractories porosity may vary between 50 and 80 per cent. moulding. 8 . burning of carbon and organic materials. decomposition of carbonates. solid-liquid • Fusion and cast or well sintered refractories may have very low porosities.

N0 . How do we account for this non-ideality? The residence time distribution (RTD) or more precisely the E(t) function may be looked upon as a correction factor to account for the non-ideality. The three basic reactor models viz. Concept The main objective of this experiment is to introduce the concept and measurement of residence time distribution and to emphasize its use in the reactor design. The time the atoms have spent in the reactor is called the residence time and the distribution of the various atoms coming out the reactor with respect to time is called the residence time distribution. Since. or atom. Pulse and step inputs are the two commonly used methods of injection.2) which. into the reactor at some time t=0 and then measuring the tracer concentration `C' in the exit stream as a function of time. v is the euent volumetric ow rate. If we now divide by the total amount of material that was injected into the reactor. owing to non-ideality prevalent in the `real' systems. The outlet concentration is then measured as a function of time. Dierent atoms take dierent time to come out of the reactor. C(t). this is not the case with the real system. batch. the conversion obtained may not be the true conversion. ∆N . The causes of non-ideality could be channeling and back mixing in the case of a PFR and dead zones and non-uniform mixing in the case of a CSTR. We often apply these models to determine the conversion and other parameters. exiting between time t and t + ∆t is essentially constant. we obtain vC(t) ∆N = ∆t N0 N0 (2. leaving the reactor between time t and t + ∆t is ∆N = C(t)v∆t (2.1) where. an amount of tracer No is suddenly injected in one shot into the feed stream entering the reactor in as short time as possible. called tracer. RTD can be determined experimentally by injecting an inert chemical. Pulse Input In a pulse input. 9 . If we select an increment of time ∆t suciently small that the concentration of tracer.2 Residence Time Distribution Objective To determine the residence time distribution in the given conguration for pulse and step inputs. then the amount of tracer material. However. The euent concentration-time curve is referred to as the C curve in the RTD analysis.. ideally all these atoms should come out of the reactor at the same time. molecule. However. there is no axial mixing in the PFR. In other words. ∆N is the amount of material that has spent an amount of time between t and t + ∆t in the reactor. Theory Imagine that 10 atoms are injected in a PFR in a short time. back mix (CSTR) and PFR are based on ideal concepts. represents the fraction of the material that has a residence time in the reactor between time t and t + ∆t.

Thus.9) Because the inlet concentration is a constant with time. t Cout (t) = C0 0 E(t )dt (2. Re-writing the above equations in the dierential form. Step Input Consider a constant rate of tracer addition to a feed that is initiated at time t = 0. C0 .11) Dividing by C0 yields Cout C0 = step 0 t E(t )dt = F (t) Thus. we have C0 (t) = 0 C0 (t) = C0 t<0 t≥0 (2.6) and integrating.12) 10 . we can take it outside the integral sign. It describes in a quantitative manner how much time dierent uid elements have spent in the reactor. Thus.8) The concentration of the tracer in the feed to the reactor is kept at this level until the concentration in the euent is indistinguishable from that in the feed.10) (2. the test may then be discontinued. the normalized concentration vs. Before this time no tracer was added to the feed.7) The integral in the denominator is the area under the C curve.3) (2. dN = vC(t)dt (2.5) (2. and so we can dene E(t) as: E(t) = C(t) ∞ 0 C(t)dt (2. The relation between E(t) and F (t) is: dF (t) = E(t) dt (2. The output concentration from a vessel is related to the input concentration by the convolution integral: t Cout (t) = 0 Cin (t − t )E(t )dt (2. we obtain N0 = 0 ∞ vC(t)dt The volumetric ow rate v is constant.4) so that ∆N = E(t)∆T N0 This quantity E(t) is called the residence time distribution function. time prole gives the F curve.For a pulse injection we dene E(t) = vC(t) N0 (2.

By using a similar analysis as shown above. we obtain the complete RTD function for a laminar ow reactor as: E(t) = 0 E(t) = τ 2 /2t3 ∞ 0 tCdt ∞ 0 Cdt t < τ /2 t ≥ τ /2 (2. The dispensing mode available with the pumps can be used to give a pulse input. the velocity prole is parabolic with the uid in the center of the tube spending the shortest time.14) (2.13) (2.17) Apparatus Figure 2. Peristaltic pumps are used to pump the water and tracer to the reactor/s. Two reservoirs are provided for the continuous phase (water) and tracer (dilute NaOH solution) respectively.15) (2.For a laminar ow reactor.1: Experimental setup The set-up consists of three CSTRs and 2 PFRs (LFRs) which can be connected in series of parallel. The concentrations at the exit of the reactor/s is/are monitored by conductivity probes.16) We can also determine the dispersion number in the following manner: Tm = = ti Ci ∆ti Ci ∆ti The variance is dened as: σ2 = t2 Ci ∆ti i − t2 m Ci ∆ti 2 σθ = σ2 t2 m 2 The Dispersion number is dened as D/uL and is given by: 2 σθ = σ2 D =2 −2 ¯2 t uL D uL 1 − expu/L/D (2. 11 .

Adjust the owrates of both the uids so that they are in the given range of residence time. ensure that the valve on the feed line is open. Plot concentration (conductivity) C vs. 13. Calculations Pulse Input 1.t. 11. Purge the tracer pump tubing with the solution from the reservoir.r.t.t. Prepare about 100 ml of 5 M NaOH solution for pulse input study. The time span can be eventually increased when the change in conductivity is not rapid. 12. Continue till the conductivity values become steady. Prior to dispensing. At a particular time instant. 6. time at every half residence time intervals. Calculate E theo (t) τ2 2t3 1 Etheo (t) = exp−t/τ τ Etheo (t) = (P F R) (CST R) 12 . 5.r. Set the ow at the maximum value so that the set quantity will be dispensed at the maximum owrate. thus. Calculate E(t) using equation 2. Activate the dispensing mode on the pump and set the quantity to dispensed. 2. 8. 7. 4. Initially (till two residence times) note down the values at every 10 sec time interval. 3.7 3. Start the ow of water through the reactors and allow the system to attain steady state (w. stop the ow of water and simultaneously start the ow of tracer. 15. 10. t 2. 9. acting as a pulse input. Continue till the conductivity values attain or approach the initial values.r. Purge the pump tubing (to be used for dispensing) with the prepared solution. Note down the conductivity values w. time at every 10 sec time interval initially followed by 30 sec later when the change in the conductivity values is not rapid. At a particular time instant press the `start' button on the pump and simultaneously start the `stop watch'. owrate).Procedure 1. Ensure that the owrate is the same as that adjusted at the start. start the ow of water through the reactors and allow steady state to be attained. Check whether both the reservoirs (water and tracer) are full. For step input study. Measure the volume of the reactors in the given conguration. Note down the conductivity w. 14.

Step Input 1. σθ and D/uL using equations 2. 4. Plot Eexp (t) and Etheo (t) vs. 6.4. Plot Eexp (t) vs. Plot concentration (conductivity) vs.12. Obtain the equation for the F-plot by curve tting. Calculate and plot Eexp (t) and Etheo (t) for given conguration.17 [only in the case of LFR] 7. Evaluate Ftheo (t) using equation 2. Evaluate Ftheo (t) for given conguration and plot Ftheo (t) and Fexp (t) vs. Dierentiate this with respect to t to obtain Eexp(t) . Calculate the mean residence time (tm ). C/C0 and Ftheo (t) vs.e. 5. 5. t. Plot Fexp (t) i. t. 2. 3. Calculate variance (σ 2 ). Results Single reactor τ tm D/uL Conguration Comments 13 . t. t. 2 6. 7.15-2. t.

The simulation studies on the butyl acetate synthesis have also indicated that this option can be better than conducting the entire reaction in a reactive distillation column. Hence. 14 . Moreover. the industrial application of reactive distillation did not take place before the 1980's. column hardware design. diusion and chemical kinetics. better heat control. Hence. The suitability of RD for a particular reaction depends on various factors such as volatilities of reactants and products along with the feasible reaction and distillation temperature.e. the use of RD for every reaction may not be feasible. scope for dicult separations and the avoidance of azeotropes are a few of the advantages that are oered by RD. alcohol and water. mass transfer rates. the aqueous phase that forms after the condensation of the vapor is almost pure water. process synthesis. the heterogeneous azeotrope or a composition close to the azeotrope can be obtained as the distillate product. Another interesting feature of this system is that it is associated with the formation a minimum boiling ternary azeotrope of ester. Although invented in 1921. Depending on the requirement either of the phases can be withdrawn as a product and the other phase can be recycled back as reux. In reactive distillation scheme. the option of using a conventional reactor for partial reaction followed by a reactive distillation column has been reported to have oered better economics. nonlinear dynamics and control is in progress. Improved selectivity. The esterication of acetic acid with alcohols like n-butanol. The alcohol is sparingly soluble in water and the ester is almost insoluble. Exploring the candidate reactions for RD. in a typical reactive distillation column that consists of both reactive and non-reactive zones. RD being a relatively new eld. The introduction of an in situ separation process in the reaction zone or vice versa leads to complex interactions between vapor-liquid equilibrium. The present work is aimed at performing a detailed experimental investigation on a reactive distillation column operated in such a mode.3 Continuous Reactive Distillation Reactive Distillation Reactive Distillation (RD) is a combination of reaction and distillation in a single vessel owing to which it enjoys a number of specic advantages over conventional sequential approach of reaction followed by distillation or other separation techniques. isobutyl alcohol and amyl alcohol fall in a typical class of reacting systems. which is heterogeneous in nature. n-Butyl acetate is manufactured by the esterication of acetic acid with n-butanol in the presence of suitable acid catalyst. butyl acetate is the least volatile component in the system is realized as a bottom product. ethanol. Experimental Material and Catalysts The packing used in the reactive distillation column were KATAPAK-S embedded with Amberlyst15 catalyst and non-catalytic HYFLUX high eciency low pressure drop wire mesh distillation packing. itself is an area that needs considerable attention to expand the domain of RD processes. which poses a great challenge for design and synthesis of these systems. increased conversion. research on various aspects such as modeling and simulation. Butyl acetate is an industrially important chemical with wide applications as a versatile solvent. The pure ester i. eective utilization of reaction heat.

3. catalyst particles are present. and hydrogenations reaction.1: KATAPAK-S Structure HYFLUX: HYFLUX is structured tower packings made of stainless steel 304 and 316. There is a 2 mm gap between the bases of adjoining triangular channels (Fig. The sandwiches are assembled with the ow channels in opposed orientation. 3. The sandwich exists of 16 triangular channels. This results in 15 .3. plied and custom formed to meet exacting specications Fig. crimped. etherication. the liquid ows inside these packed channels. the space in between the two sandwiches is geometrically nearly equal to the inside of a packed channel. Each of these sheets is corrugated.1 ). such as esterications. resulting in a structure with ow channels of a dened angle and hydraulic diameter. are particularly useful when a moderate to large number of theoretical stages have to be accomodated in a limited height of the tower. KATAPAK-S is immobilized between two sheets of metal wire gauze. A single triangular channel has a base of 36 mm. When taking two of these sandwiches and placing them together. bubble columns or reactive distillation processes. no catalyst particles are present in the open channels. and a height of 18 mm.KATAPAK-S: KATAPAK-S (S implies Sandwich) is a structured catalyst support for use in gas-liquid reaction systems such as trickle bed reactors. The open structure formed due to the proprietary lay of the laments. so that the resulting unit is characterized by an open cross-ow structure pattern. It is suitable for many catalytic applications. HYFLUX is manufactured from a multitude of ne metallic wires which are knitted into a tube which is attened. the unique stitches employed and the special crimping and plying form tortuous channels for liquids which can continuously combine. The gas ows through these open channels. Figure 3. Inside such a sandwich. divide and recombine for optimum mixing and contact with vapour. forming "sandwiches".2). with a total of 32 cross-overs. in which catalyst granules can be embedded (Fig. The channels that will be formed by this space are referred to as the open channels. 3.

Figure 3.2: Reconstruction of KATAPAK-S.3: HYFLUX noncatalytic Packing 16 . a set of intersecting triangular tubes Figure 3.

05 . butanol. The feed is preheated before introducing it to the column. All the sections are 1m tall in height. A proper insulation with external wall heating arrangement was provided to minimize the heat losses to the surrounding. In the condenser.) equipped with thermal conductivity detector (TCD). The middle reactive zone was packed with Sulzer KATAPAK-S packing embedded with ion exchange resins Amberlyst-15 as a catalyst. Temperature sensors Pt 100 are provided at dierent locations in the column to measure these temperatures (Position 1. Phase separator with the condenser is used to provide reux to the column and to continuously withdraw water formed during the reaction. The reboiler (3 lit) was externally heated with the help of a heating mantle. an aqueous phase i. almost pure water and an organic phase containing water. An electronically driven metering pump is used to transfer the liquid from the feed tank to the column. Analysis The samples were analyzed using Gas Chromatograph (GC. Mak Analytica India Ltd. C-911. Injector and detector 17 . butanol and butyl acetate. two immiscible phases are formed.e. butyl acetate and water or an equilibrium mixture from the batch reactor is fed continuously to the column through a rotameter. The unique interaction results in high mass transfer rates (maximum separation eciency) while maintaining low resistance to ow (low AP / theoretical stage).4.2.Position 8). The column used for the analysis was porapack-Q with hydrogen as carrier gas at the ow rate of 20 ml/min.0.intimate mixing between vapour passing upward through the controlled interconnecting passageways and the thin lm of liquid owing down the capillary wire network of the packing. The non-reactive rectifying and stripping sections were packed with Evergreen HYFLUX packing made out of ne metallic wires.75 F factor (m/s <0. Specications HETP ≥ ≥ 100 to 200 mm in production columns 75 mm in pilot/laboratory stills 10 in production columns 13 in pilot/laboratory stills 0.75 mm Hg 0.7 m 3 /m 2 h 3 to 8 (w/w) √ kg /M3 ) NTU/metre ≤ ≤ ∆P / theoretical plate : : : : Vapour load Liquid load Liquid holdup Apparatus and Procedure The experimental setup of a laboratory scale reactive distillation plant is as shown in Figure 3.2 . A 3m tall distillation column of inside diameter 54 mm that operates at atmospheric pressure was used. The reaction mixture consisting of acetic acid.

Figure 3.4: Experimental setup 18 .

were maintained at 220◦ C and 150◦ C respectively. Measurements 1 2 3 4 5 6 7 8 Feed Flow Rate Top Flow Rate Bottom Flow Rate Feed Composition Conversion Purity Reboiler Duty Strength of NaOH solution Values Units Steady State Column Prole Stage Wall temp Column temp Titer Value Acetic acid conc.N. The oven temperature was maintained isothermally at 240◦ C to get best resolution in less time. The samples were also analyzed by titrating them against NaOH using phenolphthalein as indicator. The results obtained by GC were conrmed by independent titrations using standard sodium hydroxide solution. Observations S. 1 2 3 4 5 6 7 8 Top 19 .

pipette. other copper salts. We can determine the chemical potential of the salt as µ = pµ+ + qµ− = pµ0 + qµ0 + pRT ln a+ + qRT ln a− + − m+ = pµ0 + qµ0 + pRT ln + qRT ln + − m0 + m− m0 − + pRT ln γ+ + pRT ln γ− (4. µi of the constituent species. For an electrolyte species ai can be expressed in terms of the molality of the ion: ai = γi mi m0 i (4. In the solution. volumetric ask. The standard state is chosen as a ctitious state where γi = 1 (corresponding to the ideal solution where all the interactions are extinguished). mol/kg of solvent. beakers.4 Verication of Debye-Huckel Theory Aim To determine experimentally the activity coecient of cupric ions in aqueous solutions and compare them with those estimated using Debye Huckel theory.4) 20 . m0 is (but not always) actually chosen as 1 i molal. It is therefore necessary to measure and predict the chemical potential of species in the solutions.1) where µ0 is the chemical potential of species i in the standard state (arbitrarily chosen). Theory Thermodynamic state of the solution can be characterized by the chemical potential. an electrolyte dissociate into cations and anions Mp Xq → pM Z+ + qX Z− pZ+ + qZ− = 0 (4. Apparatus Ion meter provided with cupric electrode. i and γi is the activity coecient of i. copper sulphate (CuSO4 .5H2 0). cations are surrounded by anions and vice versa.3) Due to electrostatic interactions. m0 is the molality in the solution at standard state. It is convenient to express chemical potential µi in terms of its activity ai dened as µi = µ0 + RT ln ai i (4.2) where mi is the molality of i. it is not possible to determine chemical potential of the individual ions. The activity coecient is the measure of the interaction of species i with the other species in the solution. For the equilibrium of the phases in contact. the chemical potential of each of the species should be equal in all phases. automatic temperature compensator. The gradient of the chemical potential provides the driving force for the diusion of the species. R is the i Universal gas constant and T is the temperature.

9) It is generally agreed to use m0 = 1.We dene as the mean activity coecient. B is not a universal constant but depends on the nature of the cations and anions.6) where µ+ = µ0 + RT ln + µ− = µ0 + RT ln − m+ γ± m0 + m− γ± m0 − (4.04.10) At 25◦ C.509. and A= 0. Thus p q γ± = γ+ γ+ 1 p+q (4. 21 .7) The above equation allows us to express the chemical potential of individual ions in terms of the mean activity coecient. Beyond this point the following equation holds. The test of the theory is to plot log γ± versus I/m0 . log γ± = |z+ z− |A 1+B I 1/2 m0 I 1/2 m0 (4. it is to be understood that does not correspond to the individual ion but to the pair of ions ( cation and anion) Debye-Huckel Law Debye-Huckel theory has been developed for very dilute ionic solution in which electrostatic interactions dominate. Hence B needs to be regressed from the experiments.11) However.509 (T /298)3/2 (4. The following equation has been derived based on the mean eld and point charge assumptions log γ± = −|z+ z− |A I m0 1/2 (4. The theory neglects all other interactions.5) m− m0 − µ = pµ0 + qµ0 + pRT ln + − = pµ+ + qµ− m+ m0 + + qRT ln + (p + q)RT ln γ± (4. The plot should be the straight line . the value of A is 0. However. This is indeed true up to m/m0 = 0.8) Where I represents the ionic strength of the solution and is given by I= 1 2 2 m + z + + m− z − 2 (4.

2.303 × 103 RT mi log + |z+ z− |A zi F zi F m0 i (4.19) At higher concentrations where E ∗ is the value extrapolated from the above equation . This electrode adsorbs specic ion.303 × 103 RT |z+ z− |A zi F mi m0 i I m0 1/2 (4.18) (4. E is the potential of the electrode (mV) and E0 is the reference potential. 2. E = E0 + 2. The Nernst equation governs the electrode potential.16) and the intercept is E0 . One reason is the dynamics of the electrode.17) We obtain the slope and the intercept of the modied plot E ∗ = E0 + S log (4. At high concentration nd B so that the modied D-H theory yields the best t to the experimental data.Measurement of Activity and Mean Activity Coecient One of the technique for the measurement of the activity coecient is to use a specic ion electrode.15) At very low concentration the activity coecient term can be neglected.303 × 103 RT (4.303 × 103 RT γ± mi log zi F m0 i I m0 1/2 (4.303 × 103 RT 2. This allows us to compute log γ± . It takes a long time for the electrode to reach equilibrium .14) 2. To correct for the second contribution we plot E ∗ = Ei − 2.12) log(ai ) zi F Where zi is the valency of the ion and F = Faraday constant. Find the slope and check whether it matches with the theory 4. Writing γ± mi (4. As a result of this adsorption .303 × 103 RT zi F (4. Find the region where it is a straight line. Plot log γ± versus √ I for the entire range of the concentration. The other reason is the error due to the omission of the correction. In this case the plot of E versus log mi /m0 is the straight line with slope i S= 2. 3. 22 . E − E∗ = log γ± S Vericationof Debye-Huckel Theory 1.13) ai = m0 i E = E0 + we get E = E0 + At very low concentrations. the potential of the electrode changes in proportion to the chemical potential of the ion in the solution . The slope of the plot deviates somewhat from the above equation.

Preparation the solution of 10000 ppm (0. note down the reading shown by the meter. 5000. From that solution prepare the solution of 1. 6.20) C Compare the experimental value of activity coecient with those calculated using Debye Huckel theory. 6000. 2. It is advisable to start with the solution of lower concentration and move onto the higher concentrations in the ascending order. 8. 3000. 6. Follow the same procedure as above and measure the potential of all solutions. Immerse the electrode in 1 ppm solution. 10000 by serial dilution. 8000. 7000. Plot the potential at lower concentration (1. Plug the Cupric electrode (lled with lling solution) to the ion meter. 7.5 H2 O. 3. 4. This results in an approximate straight line given by the Nernst equation E = E0 + 2. blot dry with tissue paper and immerse in the next solution (2ppm).303 RT log C zF The intercept of the line with the Y axis gives E0 . 10. 1000. One should wait for at least 3 minutes or till the meter shows ready whichever is longer.10 ppm) on a E versus log C . Then note down the potential reading as shown in the meter. At higher concentrations. 9.Procedure 1. 7. Then take out the electrode. the potential is given by E = E0 + 2.16M) Cu++ from CuSO4 . 4. The activity coecient is then calculated a γ= (4. 2. 3. Rinse the electrode with distilled water and wipe with a tissue paper. 5. 9000. 23 . rinse it with distilled water. 5. 100.303 RT log a zF In this equation a is the only unknown and can be calculated.

Value of E0 = 2. Concentration (ppm) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1 2 3 4 5 6 7 8 9 10 100 1000 3000 5000 6000 7000 8000 9000 10000 log C E (mV)s log a a γ (expt) = a/C Observations: 1. Value of slope = 24 .N.Data Sheet for D-H Theory Observation Table for experimental method S.

Observation Table for theoretical method S.N. Conc. B = 25 . (ppm) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1 2 3 4 5 6 7 8 9 10 100 1000 3000 5000 6000 7000 8000 9000 10000 Molar conc (m) I (ionic strength) √ I log γ γ (D-H limiting) Observation: 1.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 γ (expt) γ (theo) 26 .Results S. N.

monomers are mixed. Its dissolution would require rupture of C-C bonds. which remain suspended. and a polymerization catalyst such as benzoyl peroxide is added. The degree of cross-linking determines the mesh width of the matrix and thus the swelling ability of the resin and the mobility of the counter ions in the resin. In the case of Amberlyst. Theory Ion Exchangers Of all dierent natural and synthetic products which show ion exchange properties. and mechanical stability and the ion-exchange behavior of the resins depend primarily on the structure and the degree of cross-linking of the matrix and on the nature and number of xed ionic groups. which in turn determine the rates of ion-exchange in the resin. Thus resins are insoluble in all solvents by which they are not destroyed. It is a highly porous. consists of an irregular. an organic solvent which is a good solvent for the monomer. 27 . while the framework of an anion exchanger can be regarded as a polycation. COO− in cation exchangers and NH+ . The matrix carries ionic groups such as SO−− . but a poor solvent for the polymer is added to the polymerization mixture. Ion Exchange Resins These constitute the most important class of ion exchangers. macro reticular ion-exchanger prepared by a variation of the conventional pearl-polymerization technique. They consist of a framework held together by chemical bonds or lattice energy which carries a positive or negative surplus charge. physical. The matrix of the resins is hydrophobic. Amberlyst-15 with sulphonic acid functionality is our resin of interest. In pearl polymerization. 3 3 2 Ion exchange resins are thus cross linked polyelectrolytes. The chemical. The matrix is elastic and can swell by taking up solvent . Linear hydrocarbon macromolecules with such molecules are soluble in water. The mixture is then added to an agitated aqueous solution kept at the temperature required for poymerization. macromolecular. An ion-exchange resin is practically one single macromolecule . NH+ in anion exchangers. However. and determine their capacity by batch and continuous ow processes. For example. ion-exchange coals. hydrophilic components are introduced by the incorporation of ionic groups such as SO3 H. and synthetic inorganic exchangers. Counter ions of opposite charge move throughout the framework and can be replaced by other ions of same sign. A suspension stabilizer is added to prevent agglomeration of droplets. mineral ion exchangers. 3-D network of hydrocarbon chains. The mixture forms small droplets.5 Ion Exchange Columns Aim To plot the breakthrough curve of strong acid cation exchange Amberlyst resins. the most important are ion-exchange resins. Ion exchangers owe their characteristic properties to a peculiar feature of their structure. Highly cross linked resins are harder and more resistant to mechanical breakdown. the framework of a cation exchanger can be regarded as a macromolecular or crystalline polyanion. Their frame-work called the matrix. So ion exchange resins are made insoluble by introduction of cross-links which Interconnect the various hydrocarbon chains. a fact referred to as "heteroporosity" or "heterodictality".

and for use in the numerical calculation of ion-exchange operations. one can exploit the preference of an exchanger for highly charged ions in dilute solutions. For eg. the selectivity due to the properties of the ion exchanger (such as acidity. an appropriate complexing agent has to be added to the aqueous phase: the selectivity attained is then either due to the dierence in the stability constants or to the dierent charges or structures of the complexes formed.. Capacity and related data are primarily used for two reasons:. Large counter ions may be sterically excluded from the narrow pores of the ion exchanger All these eects depend on the nature of the counter ion and thus may lead to preferential uptake of a species by the ion exchanger. the solvent molecules are squeezed out by the growing copolymer regions. In addition to electrostatic forces. Increased selectivity can be brought about in many ways. other interactions between ions and their environment are eective. Capacity (Maximum capacity. and the degree of cross linking ) is not sucient for ensuring eective separation.for characterizing ion-exchange materials. 3. Selectivity Ion exchangers prefer one species over another due to several causes : 1.As polymerization progresses. spherical beads with wide pores are obtained. which is used for theoretical studies. The electrostatic interaction between the charged framework and the counter ions depend on the size and valence of the counter ion. dened by α= ma mb C Cb x xb = a = a ma mb Ca Cb xa xb ¯ |Z | ¯ |Z | MA B MB A ¯ |Z | |Z | M AM B B A (5. Capacity Capacity is dened as the number of counter-ion equivalents in a specied amount of material. The ability of the ion-exchanger to distinguish between the various counter ion species is called selectivity. In such a case. ion-exchange capacity) Denition : Number of inorganic groups per specied amount of ion-exchanger 28 .2) The selectivity of the ion exchange process depends on the properties of the ion exchanger used and the composition of the aqueous phase . Capacity can be dened in numerous ways: 1.1) The molal selectivity coecient . or one can choose a chelating resin. In this way. 2. basicity. is dened as A KB = (5. In the case of two ions having the same charge and very similar radii. Separation Factor The preference of the ion exchanger for one of the two counter ions is often expressed by the separation factor.

Units : meq/g dry H+ or Cl form (apparent weight capacity). b = fractional void volume of packing W = water content of the resin in weight percent d = density of the swollen resin in grams per ml B The molality of xed groups in meq/g is m= (100 − W ) × Qw W × (1 + Qi− M Qw × 10−3 ) The molarity of xed groups in meq/ml is X= d × (100 − W ) × Qw 100 × (1 + Qi− M Qw × 10−3 ) Batch Process Apparatus Stirred tank reactor with stirrer. conc.2.) Used in theoretical treatment of ion-exchange phenomena A Qv = (1 − b) × d × (100 − W ) 100 × Qw Qv = volume cpacity in equivalents per liter packed bed. Useful Capacity Denition : Capacity utilized when equilibrium is not attained Used at low ion-exchange rates Depends on experimental conditions (ion-exchange rate. volumetric asks 29 . Sorption Capacity. resins. Depends on operating conditions 8. Scientic Weight Capacity Units : meq/g dry H+ or Cl− form 3. Apparent Capacity (Eective Capacity) Denition : Number of exchangeable counter ions per specied amount of ion exchanger. Technical Volume Capacity Units: eq/liter packed bed in H+ or Cl− form and fully waterswollen 4. ion meter. cupric electrode. taken up by sorption rather than by exchange. Concentration of xed ionic groups Denition : Number of xed ionic groups in meq/cm3 swollen resin (molarity) or per gram solvent in resin (molality) Depends on experimental conditions(swelling. per specied amount of ion exchanger 6. Breakthrough Capacity ( Dynamic Capacity) Denition : Capacity utilized in column operation. Denition : Amount of solute . test tubes ( 15). stand. Ionic Strength Adjustor (ISA). etc. copper sulphate solution.) 7. belt. Apparent capacity is lower than maximum capacity when inorganic groups are incompletely ionized . pipette. . etc.etc) 5. Qw = Scientic weight capacity in milliequivalents per gram. depends on experimental conditions (pH.

Dilute the samples to 50 ml in volumetric asks and measure their concentrations using ion meter. The amount of cupric ions consumed is calculated from the initial and nal concentrations. time. Switch on the stirrer . 7. Keep adding cupric sulphate solution to the resin.N. 63. 5. Calculations Initial concentration . 6. Plot a graph of concentration vs. Take 10 g resins and prepare a slurry with distilled water. and 127.55 ppm .Procedure 1.55) eq/g of resin Observation Table S.Cf ppm Qty. 3. 6. Charge the column with the slurry such that there are no air bubbles trapped. Calibrate the ion meter using cupric nitrate standards of concentrations 0.6355 ppm . Fit the reactor on the stand and attaché the belt to the stirrer which is adjusted on the pulleys. Continuous Process Procedure 1. of cupric ions used Q= (Cf − C0 ) × 250 1000000 Capacity of resins = (Q/63. Take known weight of resins in the stirred tank reactor. and let it ow out at approximately 1 ml/min.C0 ppm Final concentration .355 ppm . Time (min) Cu ion concentration (ppm) Graph Plot a graph of concentration versus time. Withdraw 1 ml samples from the tank using a pipette at every 40 seconds for about 10 minutes.1 ppm. 2. 30 . Pour quickly calculated volume of 800 ppm cupric sulphate solution into the tank and start the timer . 4. 2.

Results and Comments 31 . 4. Observation Table S. After every 20 ml.3. A graph of concentration versus volume is plotted .N. Time (min) Cu ion concentration (ppm) Graph Plot a graph of concentration versus time. measure out 1 ml of euent. dilute it to 50 ml in the volumetric ask and measure its concentration in the ion meter.

and • To study heterogeneous reaction between styrene and hypochlorous acid in stirred contactor and stirred disc contactor. The alternate way to produce hypochlorous acid is through reaction between hydrogen peroxide and hydrochloric acid. It is used to synthesize phenyl ethyl alcohol by hydrogenation process. people are shifting towards more environmentally friendly catalytic oxidations with either oxygen or hydrogen peroxide. Apparatus The laboratory experimental set-up for synthesis of styrene chlorohydrin consists of following reactors: 1. Most of the Propylene/Ethylene oxide in earlier days was being produced by this process. There are two steps in the process of synthesis of styrene chlorohydrin. Bubble column and Mechanically agitated reactor with chlorine gas supply 2. ne chemical industry still prefers this route for olen oxides like styrene oxide. Phenyl ethyl alcohol is used as an ingredient in perfumes. deodorants etc.6 Gas-Liquid and Liquid-Liquid Reaction Aim • To synthesize styrene chlorohydrin from styrene. • To study chlorination in bubble column and stirred contactor. chlorine is a loss as it does not appear in the nal product. Styrene oxide. Reactions H2 O + Cl2 → HOCl + HCl C8 H8 + HOCl → C8 H9 ClO (gas-liquid reaction) (liquid-liquid reaction) Application This is a typical traditional process of converting olen to its epoxide (or oxide) (Figure 6. Hence. So the chlorination of water in controlled conditions favors the reaction to form hypochlorous acid. However. The chlorohydrin produced in this process is further hydrolysed by sodium/calcium hydroxide to the oxide.1). water and chlorine. Stirred contactor and Stirred disc contactor. which is ne chemical. 32 . One must note the limitation of this process that large amount wastes such as sodium/calcium chloride is generated. in spite of being a popular route in old days. In the rst step chlorination of water takes place and hypochlorous acid forms whereas in second step heterogeneous reaction between styrene and hypochlorous acid takes place to form styrene chlorohydrin. But in this reaction chances of unreacted HCl remaining are more and that will aect second step. may also be manufactured by this route.

The process within double dotted line is to be studied in laboratory. 33 .1: The ow sheet for production of olen oxide.Figure 6.

Sodium thiosulphate titrant: Make 0. 2. 4. In the rst step of the process. There will be two distinct phases (lower organic and upper aqueous one). of HOCl (g/L) = 1. Calculate the conc.5H2 O). (mL) 34 . 2. Make 25 mL of HOCl sample in conical ask with ice chips to maintain low temperature. 3. Sodium thiosulphate (Na2 S2 O3 .5H2 O in 1 L of distilled water. pass chlorine gas through the sparger at the bottom of column (measure ow rate). 2.5 wt% NaOH solution (about 10 L). 3. Measure pH and analyze for HOCl concentration at various time intervals till HOCl concentration reaches 30 g/L). The reaction is instantaneous and exothermic. 5. Prepare 2. Analyze aqueous phase for unreacted HOCl by titration method and organic phase for products by using gas chromatography (GC) with FID detector. Make an emulsion of styrene (50 mL) and water (500 mL) using high speed agitator in mechanically agitated reactor and lower down the temperature to 1◦ C by passing chilled water through jacket . Keep the record of HOCl added. This is end point of titration. Add 1 gm of KI crystals and 1 mL of starch indicator and brown colour appears. Separate the aqueous and organic phases. Procedure 1. Add acetic acid if pH is higher than 5 in such way that pH drops in the range of 3.5 N sodium thiosulphate solution by adding 125 gm of Na2 S2 O3 . 4.5 to 5. Liquid-Liquid reaction: Chlorohydrination 1. Analysis Analysis of HOCl (Titration Method) • Chemicals: • Reagents: Potassium iodide (KI crystals).05 × B. Add HOCl solution in such a way that the temperature remains 1-4◦ C till completion of reaction.R. Acetic acid 1. Starch. 3. 2. Start both the cryostats for chilling system (set temperature at -1◦ C).Procedure Gas-Liquid reaction: Formation of HOCl 1. Note down the burette reading. Starch: Boil 2 gm of starch in 100 mL of distilled water. Titrate it with sodium thiosulphate solution till the brown colour disappears. Make 10 mL of HOCl sample and measure pH (make sure it is above 4).

temperature of the column and carrier ow rate also strongly inuence the separation (or resolution) of the component. The instrument The schematic diagram of the GC instrument is shown in Figure 6. The method exploits the dierence in the anity toward a given solid (usually an adsorbent) of the various components present in the mixture. Figure 6. Hence one has to choose the right combination of these parameters while separating a given sample mixture. Hence at the detector port the component appears at dierent time interval. component is detected and a voltage signal is generated that is proportional to the amount of component present in the sample. The vaporized sample ows through the column over the stationery phase when the sample comes in contact of the stationary phase some components which have stronger anity lag behind while some with less anity ow with the carrier. that are either are in gaseous phase or that can be converted in the gaseous state (or vapor state) under the given conditions. the injector temperature is maintained in such a way that the sample. This detector can only detect the component that burn (e. At the detector. The column contains a stationary phase. Based on this dierence the components are separated and analyzed with the help of various detectors. Apart from the nature from a stationary phase. thermal conductivity detector. The continuous air (or oxygen) and hydrogen supply to this detector is essential for ame generation.Analysis of organic phase for styrene chlorohydrine Gas Chromatography Theory and background Gas chromatography is the technique of analysis of the components in liquid or gaseous mixture. atomic absorption detector. These times correspond to residence times of the respective components. Hence non-burnable components such as water can not be analyzed using FID. The sample to be analyzed is injected in the injector port of the column through which a carrier inert gas ows at the desired ow rate.2: Schematic diagram of a Gas Chromatograph 35 . Flame ionization detector (FID) The component is burnt and the voltage signal is proportional to the concentration of ion generated.2. such as ame ionized detector.g. if in a liquid form is vaporized at the injector port. hydrocarbon). since the analysis is based on gas-liquid interactions it works only for the components. The injection volume is decided based on whether it is gas or liquid sample and on the sensitivity of the detector.

05 mL) sample of ltered organic phase 3. Can you think of any other gas . Observations Table 1: The variation of HOCl concentration with time Time (min) Temp (◦ C) pH Burette reading (ml) HOCl conc. Inject (0. Take 2 mL of organic phase and lter it through a bed of sodium sulphate to remove the water from organic phase. 2. Prepare the calibration chart using authentic sample of styrene chlorohydrin. What is the necessity of NaOH in the chlorine absorber? 3.Analysis of Samples 1. (g/L) Time (min) Temperature (◦ C) Start End Styrene: Rxn time Param.area of SCH in chomratogram Questions 1. List dierent parameters involved in the process that you would like to investigate to possibly obtain the better performance? 4. Calculate the chlorine and NaOH requirements in the process? 2. HOCl (vol) (min) studied Styrene Area % (from GC analysis) 2 SCH (3) 4 5 RPM Remarks 6 Results Yield of Styrene chlorohydrin is area of SCH in chromatogram × 100% total area in chromatogram .liquid or liquid ? liquid contactor that can be used for the reactions involved? Give the relative merits and demerits? 36 .

Once the solvent is within 1-2 cm of the top of the TLC sheet. glass or aluminum sheet is coated with a thin layer of silica gel. 1cm from the bottom of the TLC plate as shown in Figure 7. Analyzing the purity of a compound. More polar analytes interact more strongly with the stationary phase in move very slowly up the TLC plate. TLC plate. Individual components move up at dierent rates. 37 . Following the course of a reaction. 4. etc. HPTLC applicator and scanner.1-A. usually silica gel) and a solvent (the mobile phase) which ows through the adsorbent. a plastic. Benzhydrol. toluene. 3. As the mobile phase rises up the TLC plate by capillary action. In TLC. Analyzing fractions collected during purication. Chemicals Benzophenone. The TLC is developed in a chamber. as well as by dipole-dipole and H-bonding. the components dissolve in the solvent and move up the TLC plate. syringe. More nonpolar analytes interact less strongly with the polar silica gel and more strongly with the less polar mobile phase and move higher up the TLC plate. Identication of components of a mixture (using appropriate standards) 2. By comparison. A very small amount of a solution of the substance to be analyzed is applied in a small spot with a capillary tube. The stationary phase is hydrated SiO2 and is very "polar". depending on intermolecular forces between the component and the silica gel stationary phase and the component and the mobile phase as shown in Figure 7. It is used for following dierent situations: 1. hexane. It is capable of strong dipole-dipole and H-bond donating and accepting interactions with the "analytes" (the components being analyzed). Apparatus Sample bottles. methanol.7 High Performance Thin Layer Chromatography Aim The objective of this experiment is to train you with the HPTLC instrument and measurement of concentrations of the components in the liquid mixtures. etc. which contains the developing solvent (the mobile phase). the mobile phase is relatively nonpolar and is capable of interacting with analytes by stronger London forces. the TLC is removed from the developing chamber and the farthest extent of the solvent (the solvent front) is marked with a pencil. A truncated lter paper placed in the chamber serves to saturate the chamber with mobile phase.1-B. In TLC. Theory High performance thin layer chromatography (HPTLC) is an important technique for identication and separation of mixtures of organic compounds. components of the mixture are partitioned between an adsorbent (the stationary phase.

The center of the spots are located and marked with a pencil and the distances between the origin and the center of the spots are measured. The spots are visualized using a UV lamp. run at the same time. These spots are shown in Figure 3. (The TLC plates we will use contain a uorescent indicator. If a compound on the TLC absorbs that light. 38 . The Rf is dened as the distance the center of the spot moved divided by the distance the solvent front moved (both measured from the origin). Two substances that have the same Rf value may be identical. and comparison should be made only between spots on the same sheet.The solvent is allowed to evaporate from the TLC sheet in the hood. which "glows" green under 254 nm UV light.1: Schematic diagram of HPTLC Procedure 1. Prepare the ve dierent concentrations of the benzophenone and benzhydrol in 2 mL of methanol or acetone. it will appear as a dark spot). those with dierent Rf values are not identical. Figure 7. Rf values can be used to aid in the identication of a substance by comparison to standards. The Rf value is not a physical constant.

(You may want to visualize your spots using the UV lamp to make sure you can see the spots before developing the TLC). Prepare the four dierent mixtures of both components (unknown compositions) in 2 mL methanol or acetone. DO NOT wash the jars with water or acetone. 3. 6. 5. Develop your TLC in toluene and hexane (50:50) solvent system. 3. 8. middle ve lanes. What are the dierent chromatography methods? Explain each method in briey. 10. spot your pure benzhydrol solution. Analyze the TLC plate by using the scanner.2. Apply the spots of prepared solutions on the TLC plate (1 cm from the bottom of the plate) by using applicator. Prepare a TLC developing Chamber. In the rst ve lanes. Present calibration curves of two components and concentrations of the two components in the given liquid mixtures. 9. Allow the solvent to evaporate from the TLC in the hood. What are the dierent manual errors encounters in the analysis using the HPTLC method? 39 . Exercise 1. 7. When the solvent has migrated within 1-2 cm from the top of the plate. empty the developing solvent into the waste jar in the hood. Remove the lter paper from the jar and place the open jar and the lter paper in your hood and allow the solvent to evaporate. remove the TLC. and last four lanes. 4. Place a truncated lter paper in the jar so that when solvent is added the solvent will wick up the lter paper and saturate the chamber with solvent. spot pure benzophenone solution. Simply allow the solvent to evaporate completely before reusing the jar for the next analysis. Add solvent to the jar to a depth of 1/2 cm. spot your unknown concentrations of liquid mixtures. What are the advantages of the HPTLC method? 4. Visualize your TLC under a UV lamp. When your TLC is complete. 2.

05M The cathodic and anodic reactions in the cells are Cu++ + 2e− → Cu H2 O → (1/2)O2 + 2H + 2e + − (cathode) (anode) The copper electro deposition is a rst-order reaction with respect to cupric ion concentration in the waste water. By measuring the amount of metal recovered and the total electric charges used in the electrolysis. Electrolytic System and Data Analysis In this experiment. and the eect of mass transport of metal ions on rate of electrodeposition reaction. a = A/Vsol . also calculate the current eciency (η ) and energy requirement of the process. 2. Composition of Electrolyte Copper sulphate (CuSO4 . The values of ka depend on ow rate of electrolyte. Evaluate the current and energy consumption of the process. determine the reaction rate constant.1. Determine the reaction rate constant of the electro deposition reaction. a plot of ln C vs t yields a straight line. By assuming a uniform concentration throughout the solution tank and electrolytic cell. Vsol = volume of wastewater in the solution tank According to equation 8. 40 . Perform the electrolysis experiment to reduce toxic metal ions (Cu++ ) from an initial concentration of 500 -1000 ppm to a low level acceptable for discharge as required by Pollution Control Board regulations. C0 = initial concentration of cupric ion. and water circulation rates.8 Metal Recovery from a Dilute Solution by an Electrochemical Method Aims Toxic heavy metal ions in wastewater can be reduced by electro deposition of metals at a cathode (Graphite) 1. k = First order reaction rate constant for deposition of Cu2+ at cathode. its activation energy. temperature and cathode potential.1) where C = concentration of cupric ion in waste water at time t. The cathode potential can be changed by varying the cell voltage. and the eect of mass transfer on the rate constant. its activation energy. wastewater circulation rate can be described by C = exp(−kat) C0 (8. and the value of ka can be evaluated from the slope. the concentration change of cupric ion at a given set of controlled anode-to-cathode cell voltage.5H2 O).Cu++ = 500-1000 ppm Sodium sulphate (Na2 SO4 ) = 0. By measuring the concentration changes of the metal ion at various controlled anode-tocathode cell voltages. where A = total area of cathode (2 dm2 ). a ow-through electrochemical cell is operated iin a recirculation mode.

(3) cupric ion concentration either by spectrophotometer or simple titration with EDTA. Energy (kWh/kg-metal) = IEcell dt 3600 × 1000W θ 0 (8. Electrolyte containing 500-1000 ppm Cu2+ and 0.1. Calculate the eective volumetric reaction rate constant ka (sec−1 ) from slope of the graph.(2) Cell voltage (Volts). Measure (1) cell current (I) in amperes. from experimental curve C vs t (sec) curve and by comparing the value to the current (I ). W = Vsol (C0 − Cf inal ) M = Atomic weight of copper (63. 41 . Results and Calculations Experiment 1 Plot semi log plot of cupric ion concentration versus electrolysis time (sec) for controlled cell voltage and ow rate of electrolyte. and (4) solution pH by pH meter.1. according to Faraday's law. Experimental Method The experimental setup is shown in Figure 8. dC/dt. Electrolysis started by applying a constant anode-to-cathode cell voltage (2-6V) from DC power supply. The average current eciency is obtained by comparing the mass of Cu recovered at the end of the experiment. The energy consumption per kg of copper recovered is calculated by integrating the current I and voltage curve with respect to the time according to. and n = number of electrons (2 equiv/mol). Average Current eciency(ηav )% = W (M/nF ) θ 0 × 100 Idt (8.4) Where Ecell = cell voltage and W = weight of copper deposited (kg).3) Where θ = Total electrolysis time in seconds and W = mass of copper deposited at the cathode. Current eciency(ηi )% = Vsol (dC/dt) × 100 I/nF (8. Show that the concentration of cupric ion decreases logarithmically with the time as in equation 8.05M Na2 SO4 prepared in tap water is circulated through electrolytic cell at various ow rates. at specic time intervals.The instantaneous current eciency (ηi ) of copper deposition reaction at a given electrolysis time can be evaluated by calculating the rate of change of cupric ion concentration.5g/mol). at the same electrolysis time.2) Where F = 96500C/equiv.

Cell voltage= (V). 2H2 O + 2e = H2 + 2OH − (8.5 4 4. Find instantaneous cathode current eciency (ηi ) and at end experiment nd the average current eciency (ηav ) by using equations 8.5) The OH ions generated from the above reaction neutralizes the H ions and thus pH changes with time. Average Current = Amp. Average current eciency (ηa ) = Time (sec) inst. current eciency (ηi ) 1800 3600 5400 7200 42 .2 & 8. This indicates ohmic resistance of the electrolyte played an important role in the copper deposition reaction. Flow rate = l/sec.5 Experiment 3 Current eciency and Energy requirement: The main side reaction at the cathode is reduction of H2 O molecules to H2 gas and OH− ions. Flow rate = Cupric ion conc.4.3 respectively. (ppm) Time (sec) l/sec Experiment 2 Reaction rate constant (ka): Plot ka versus cell voltage for series of runs at xed ow rate of electrolyte. Controlled cell voltage = V. Also calculate the energy requirement by using formula 8. Flow rate = l/sec Cell voltage (V) ka (sec−1 ) 3 3. Change the cell voltage after 1800 sec intervals and measure ka. Show that value of ka varied linearly with cell voltage as described by Ohm's law.

Press "Zero" key. Wait for the self-test to nish 2. Adjust the wave length as displayed (810nm) by rotating the knob on right hand side of instrument. Now replace the blank solution vial with the vial containing unknown Cu2+ solution. Log-log plot of the eective volumetric reaction rate ka (sec−1 ) versus ow rate of electrolyte should give a straight line. this suggests that the copper deposition from dilute solution is under a mixed control of mass transfer and ohmic resistance of the electrolyte. 984. 43 . Press I/O. Increasing the solution velocity near cathode enhances the mass transfer rate. 6. for a controlled cell voltage. 5. Press "Enter" key. 3. Enter the program no. the rate-controlling step is generally the transport of metal ions from the bulk solution to the cathode surface. 4. the reaction rate constant would be expected to be independent of the cell voltage. and press "Read" key. Place Zero or Blank sample vial in cell compartment put the vial cover. The fact that ka increases with increase in both cell voltage and ow rate. This linear relationship shows a strong mass transfer inuence on the rate of the copper deposition in the present system. Cell voltage = Volts. Spectrophotometer will display the concentration of Cu2+ in ppm. Average Current (I) = Amps log ka (sec−1 ) log ow rate Estimation of Cu By Spectrophotometer 1. 8. 7. But if the copper deposition reaction is controlled by mass transfer. Place the vial cover. Switch on the Spectrophotometer DR/2010.Plot instantaneous cathode current eciency (ηi %) versus time. The average current eciency (ηav ) can be calculated by integrating the ηi with respect to time and dividing the result with the total electrolysis time of an experimental run. Experiment 4 Mass Transfer Aspects of Electrodeposition Reaction: For electrodeposition of metal from a dilute solution.

Add 20 ml of distilled water. Page 144-155 Figure 8. 2002.By EDTA titration method 1.5 ml) till solution turns deep blue.1: Electrolytic Cell for Copper Recovery from a Dilute Solution 44 . 2. 8. 3.05M EDTA = 3.177mg of Cu Reference: Chemical Engineering Education.05M EDTA solution.01mol EDTA = 0.01M/0. Titrate against 0. 4.1. Pipette out 20 ml of electrolyte from cell outlet in 250ml conical ask. Add 4-5 drops of aqueous solution of Fast Sulphon Black-F indicator.then 1 ml of 0. Add few drops of ammonia (1 . 7.6354mg of Cu. 5. End point of titration is when colour changes from blue to green. If EDTA is 0. 6. 1ml of 0.05M.

which is one of the metal ion catalysts. peracid. however. cathode.1: 1) Electrolytic cell. a wave length where only Mn(III) is absorbed. has a special signicance because of its use as oxidizing agent for the synthesis of organic compounds. and 3) bath composition in electrolytic preparation of Mn(III) acetate in laboratory. 7) DC Source At a particular intervals the out is collected and Mn (III) is routinely determined either by UV spectrophotometry at 456nm. obviating the use of additional chemicals. by peristaltic pump. 2 & 3) Inlet & Outlet for electrolyte 4) Perforated Graphite anode.4H2 O] by common oxidizing agents such as. Approach The packed-bed reactor as shown in Figure-9. When required ow rate adjusted and current is supplied to the cell. Potassium permanganate. A known composition of electrolyte is introduced into the reactor from the bottom.2H2 O] can be regenerated from. 2) Current density.1 is for electro-synthesis of Mn (III) acetate. it can be generated electrolytically. manganous acetate [(CH3 CO2 )2 Mn.9 Electrosynthesis of Manganese (III) Acetate in a Packed Bed Reactor Introduction The use of metal ion catalysts for oxidation of aromatic hydrocarbons is well established. Figure 9. Aim To study Eect of. 5) Carbon Particulates. 1) ow rate of electrolyte. More attractively. and lead (IV) oxide. or by treating with measured excess of ferrous ammonium sulphate solution and back titration with standard potassium dichromate solution. The manganese (III) ion is generally used in the form of acetate. there by. The manganic acetate [(CH3 CO2 )3 Mn. 45 . 6) Perforated Ti. Manganese (III) ion.

(πdl + 2πr2 ) 2. Find average area. Observations and Calculations Experiment 1: Eect of current density on current eciency Given: 1) Bath Composition: 2) Flow rate = −2 ) Time (sec) Current density (mA cm Current eciency η % 1800 3600 5400 7200 46 . Take 15-20 carbon particulates.4H2O Sodium Acetate Acetic acid (Conc.1) As a competing reaction oxygen is evolved. (usually ow rate is 1 ml/min to 5 ml/min) 4. 2OH − → (1/2)O2 + H2 O + 2e− (9.3) Experimental Procedure Prepare the following solution of known composition. Introduce carbon particles in electrolytic reactor. Allow to ow the solution. Start the peristaltic pump.2) The reaction occurring at the cathode is. H + + e− → (1/2)H2 (9. Collect the outlet solution. about 100-200ml 1. 3. Pass the current. 2. 4. Find the surface area of about 5-6 particulates. nd the concentration of Mn (III) acetate either by titration method or by spectrophotometer.Electrolytic Reaction The regenerative oxidation occurs at the anode according to the reaction: M n(II) → M n(III) + e− (9. These particles will rest on perforated graphite anode.) Water 80-100mM 400-470mM 90-95% 10-5% 1. so that it should not touch carbon particles. Introduce perforated Titanium Cathode from the top of reactor. 3. Mn(II) acetate.

E is applied voltage. UV Spectrophotometric method At wavelength 456 nm only Mn (III) absorbs.1N Ferrous Ammonium Sulphate 3. Find the unknown Concentration. where ∆c is the amount of Mn (III) acetate (mol). F is Faraday constant (Amp. n is the number of electrons involved in electrode reaction The Energy consumption Ec can be calculated as Ec = nF E/M Ce Estimation of Mn(III) by back titration 1.Experiment 2: Eect of ow rate on current eciency Given: 1) Bath Composition: 2) Current density (mA/cm2 ) = Time (sec) Flow rate (ml/min) Current eciency η % 1800 3600 5400 7200 Calculation of current eciency Current eciency Ce (η) = 100∆cηF/It t./mol/e). M is Molar mass of Mn (III) acetate (kg/mol). Titrate against 0. 47 . Add 1-2 ml of conc. Prepare a calibration chart for various known concentrations of Mn (III) solution. 4. sulphric acid & 1-5drops of N-phenyl anthranalic acid as indicator. Add known volume of (in excess) 0. 5. t is the electrolysis period in seconds. Pipette out known volume of electrolyte. 2. It is the total current in ampere. Colour change is from green to violet red.1N Potassium dichromate.

dp = eective particle diameter. ft. and particularly in the case of uidized beds.2) (10. The liquid rich in the soluble species is taken out at the bottom. and ows upward. the pressure drop per unit length of packing.2 . Theory Chemical engineering operations commonly involve the use of packed and uidized beds. wetting the packing material.1) where ∆P = pressure drop.-ft. lb. These are devices in which a large surface area for contact between a liquid and a gas (absorption. we only focus on the pressure drop issue.)). Pressure drop in the irrigated packing as continuous range: G2 ∆P = m × 10−8 10(nL /ρl ) Z ρg dp = 6(1 − ) ap (10. The liquid is distributed as uniformly as possible at the top of the column and ows downward. contacting the liquid in a countercurrent fashion.) (centistokes × 0.-ft. From a uid mechanical perspective.(centipoise × 2.42 = lb./hr. ft. distillation) or a solid and a gas or liquid (adsorption. 48 ./hr.2 ρg = uid density.-ft. catalysis) is obtained for achieving rapid mass and heat transfer. catalytic chemical reactions. lb. The term. Here. You will nd a good deal of information about ow through packed and uidized beds in the book by McCabe and Smith and Perry's Handbook (1997). dimensionless gc = acceleration of gravity (32./hr. The soluble species is absorbed in the liquid. Other uid mechanical issues involve the proper distribution of the liquid across the cross-section. To calculate this quantity we rely on a friction factor correlation attributed to Ergun. Pressure drops are correlated in terms of (∆P/L).3876 × density.10 Hydrodynamics of packed columns Aim To study the pressure drop and ooding characteristics in a packed column. Here. A gas is admitted at the bottom. Pressure drop for the dry packing is calculated by ∆P gc 3 dp ρg A(1 − ) = +B 2 Re Z(1 − )G (10. A typical packed bed is a cylindrical column that is lled with a suitable packing material.-ft. lb.2 ft/s2 . the most important issue is that of the pressure drop required for the liquid or the gas to ow through the column at a specied ow rate. Here./hr. we can discuss the experimental analysis to nd out pressure drop and ooding characteristics in a packed column. Design of packing materials to achieve uniform distribution of the uid across the cross-section throughout the column is an important subject as well. and the lean gas leaves the column at the top. (µ = uid viscosity. lb/ft3 .. An example of a packed bed is an absorber. lb. = interparticle void fraction.3 = lb. G = ρV = gas velocity./ft. (∆P/L). or psi. and developing models of the velocity prole in the liquid lm around a piece of packing material so that heat/mass transfer calculations can be made. Z = depth of the packed bed./in. is usually expressed as "psi per foot of packing".3) where packing surface ap is in (m2 /m3 ). the gas contains some carrier species that is insoluble in the liquid (such as air) and a soluble species such as carbon dioxide or ammonia.

(d) Cut o the air ow and again repeat the procedure 3a. 5. Introduce the air at a small ow rate. 3. in the manometer. Pressure Drop in the Irrigated Packing: (a) Stop the gas ow and ll the water in the column to be completely submerged and wet the packing. (c) Void fraction: Fill the column with the water so as to completely submerge the packing. (c) Increase the gas rate while keeping the liquid rate same and record the manometer readings. (b) Increase the air ow rate and again record ∆P vs. When the packing is completely wet drain o the water. This procedure has to be repeated for at least ve liquid ow rates covering the whole range of the manometer. (b) Column diameter: Fill the water in the column and rain a measured empty height in a measuring cylinder. Drain the water and collect the water volume drained as the water level falls from the top to bottom of the packing. Dry Packing Pressure Drop: (a) Introduce the air into the column at a low ow rate without the liquid ow.Experimental procedure 1. Take minimum six reading by increasing the gas ow rate. (b) Adjust a small water ow rate and allow it to run for a few minutes. (c) ∆P/Z vs. Observation and data presentation: (a) Data from the literature: (For the packing:) (1) (2) = ap / (wet packed) = (b) Calibration data of ow rate vs. ∆P to be provided. Record the pressure drop across the packing ∆P in the manometer C and air ow rate in the manometer A. A minimum six gas rates covering the whole gas ow range have to be taken for each liquid rate. 3b and 3c for an increased liquid rate. 2. 49 . covering the whole range in the manometer C. Allow the gas to run for 5 to 10 minutes till the liquid columns in the manometers are stabilized. The column in diameter D can be calculated. Check that the liquid in all the manometers is at the equal levels. Allow the air bubbles to escape. G. (d) Measure the geometrical dimensions of the packing and calculate ap and other important packing properties. Allow the system to come to steady state and take the readings. Measurement of the packing properties: (a) Measure the height of the packing (Z ) by a scale. with L parameter. gas ow rate. Calculate the void fraction ( ) from this. 4.

2 with the help of generalized correlation: a log L G ρg ρl 1/2 vs log p G 2 3 µ0. and gc is the acceleration of gravity (32. Calculate and report the following: Height of the packing Z (m): Calculate column diameter D (cm): Void fraction : Types of the packing: Nominal packing diameter Height of other geometrical dimensions: Packing surface = ap : Packing factor (from literature and calculated): Conclusions and Comments 1. Note that Y is not dimensionless ap is a packing surface factor found in Perry Table 18-5 (ft−1 ).2 ft/s2 ).0 ft3 /min at STP.m2 ∆P/Z L0 min gas rate kg/cm2 /m L1 (min 5 ow rates) 6. Give your comments on the results and possible sources of errors and precautions. G is the gas mass ux (lbm/ft2 s). Figure 18-39)).0926lbm/ft2 s 50 . consider an air ow rate of 6. µl is the liquid viscosity (centipoises). ρg is the gas density (lbm/ft3 ).Liquid ow (kg/hr. 3.2 ]/(ρg ρl gc ) (see Perry's Handbook (Fifth Edition. As an example.2 l gc ρg ρl Here L is the liquid mass ux (lbm/ft2 s) based on the area of the empty column. G plots identify and report (a) The ooding and loading points (b) Critical liquid ow rate. 2. a water ow rate of 1200 g/s.1 and 10. ρl is the liquid mass density (lbm/ft3 ). Plot (∆P/Z ) vs. and a column ID of 4 inches (corresponding to a column area of 0.2. Report the slope of (∆P/Z ) vs.m2 ) Gas ow (kg/hr.5 and the ordinate Y is = [G 2 (ap / 3 )µ0.0872 ft2 ). Sample calculation of Pressure drop We have a plot in which the abscissa X is X = (L /G )(ρg /ρl )0. G and compare with that in equations 10.0872) = 0. G on a log-log plot with L including L = 0 as parameter. With the L and G values at the ooding point found in 10. 4. G = ((6 × 29)/(359 × 60))(1/0. Calculate the dynamic (ap / 3 ). and compare with the values calculatedand reported in the literature. From (∆P/Z ) vs.

φ = 1.2) = 0.0740/62.0578 Based on Figure 18-39 in Perry. Chemical Engineers Handbook.0926)(0. McGraw Hill Book Company.5 = 0.L = 1200/(453. Fp = 1000 (1/ft).6 × 60 × 0.3 × 32.40 inches of water.0872) = 0. Editor.506lbm/ft2 s µ = 1. Unit Operations of Chemical Engineering.3)0. 21-19 (1973). J.2)/(0.715 (1976). McCabe and Smith. pp. Y = (0. References 1. 5th Edition. 2. 709.2/298.506/0. the gas phase pressure drop per foot of packing is about 1. H.2) = 0.3 lbm/ft3 .. Perry.0 centipoise. ρl = 62.0740 lbm/ft3 and X = (0. ρg = (29/359)(273. 3rd Edition.5 inches of water.188.074 × 62. If the packing height is 30 inches the predicted pressure drop is 3.09262 × 1000 × 10. pp. 51 .

6) where. Material Balance The rate of depletion of liquid is equal to the rate of distillate output. the vapour at any time is in equilibrium with the liquid from which it rises but changes continuously in the composition.7) (11.5 can be solved analytically (provided the relationship between y ∗ and x is available) or graphically (calculating the area under the curve for the plot of 1/(y ∗ − x) vs x.out = accumulation 0 − dD = dL (11.1) Taking balance on more volatile component. Assume that L mol of liquid in the still of composition x mol fraction A and that an amount dD mol of distillate is vaporized. The instantaneous rate of depletion of a component in the liquid is therefore.4) (11.2) (11. of mol fraction y ∗ in equilibrium with the liquid. Thus. In .3) (11. F W dL = L xF xW y∗ dx −x This equation can be integrated to get the following form which is called the Rayleigh's Equation. W and xw can be obtained by material balance. 52 . 11. W = moles of residual liquid of composition xW .5) Therefore rearrangement gives. 0 − y ∗ dD = d(Lx) 0 − y ∗ dD = xdL + Ldx y ∗ dL = xdL + Ldx (11.8) The integral in eqn. the mathematical approach used must be dierential. F = moles of feed of composition xF . F =D+W F xF = DxD + W xW (11. ln F = W xF xW y∗ dx −x (11.11 Dierential Distillation Aim To verify the Rayleigh's equation for a dierential distillation in a binary system Theory In the case of a dierential distillation.

Moelcular weights of A and B . η12b ). Densities of A and B . Observations and Calculations Data from the literature 1. Measure the RI of the bulk from each of the asks (eta1b . After approximately 30 ml of the distillate has been collected. w12 ). 2. eta2b . Measure the refractive indices (RI) of the samples collected in the test-tubes (η1t .1: Schematic of the setup Procedure 1.. . 6.. This procedure should be repeated for collecting 8 distillate samples. Weigh 8 nos. 4. refractive index (h) of pure components A and B . Prepare a calibration plot of mole fraction (x) vs. 2. Start the ow of water through the condenser. remove the ask and collect next 8 to 10 drops of the distillate in tagged test-tube and then put another ask for the collection of the distillate. 5. When the mixture starts boiling... 300 ml) volume of the distillation ask with a mixture of A and B of known composition (xF ). w2 . Fill 3/4th (approx. of tagged stoppered conical asks.Apparatus Figure 11. 53 .. Start heating at a slow rate.. Vapour liquid equilibrium data for A and B at atmospheric pressure..η12t ). η2t .. collect the distillate in a weighed 50 ml ask. Refractive indices of A and B . The mixture is weighed (w) before charging in the distillation ask. 4. 3.. 3. Weigh the samples collected in the conical asks (w1 .

.9 1.5 0.8 0.2 0.6 0. Mole fraction of A 1 2 3 4 5 6 7 8 9 10 11 Calculations RI 0 0. Calculate D (amount of distillate) (from weighed 30 ml sample) and xD (distillate composition) (from refractive index of 30 ml sample) for each sample.3 0.N. + ln(F/W )8 54 F xF D xD W xW y∗ x ln(F/W )i 1/(y ∗ − x) ..) 4.8 for each fraction. Calculate y ∗ (vapor phase composition) for each sample (from Refractive index of 8 drops collected. Complete the following Table.4 0. RI S. 3.0 1. S. 2.Calibration data for mole fraction vs. Calculate x (liquid phase composition in equilibrium with y ∗ ) using Raoult's law. Calculate W (amount of residue still left in the ask) and xW (composition of residue) using Eqn. 5.7 0.1 0. 11.7 and 11. 1 2 3 4 5 6 7 8 6.N. Calculate ln(F/W ) = ln(F/W )1 + ln(F/W )2 + .

8. Plot 1/(y ∗ − x) vs x and measure the area under the curve. Calculate % Error = ln(F/W ) − xF xw dx/(y ∗ − x) ln(F/W ) × 100 55 . Now verify Eqn. 11. 9.6.7.

**12 Distillation with Total Reux
**

Aim

To determine the overall eciency of the plate column, operating under total reux for a binary system and number of transfer units for a packed column.

Theory

Overall eciency = Fenske's equation is

log NM + 1 = αav =

XD 1−XW 1−XD XW

Number of theoretical stages Number of actual stages

(12.1)

log αav αtop × αbottom

(12.2) (12.3)

NM = number of theoretical stages at total reux, and αav = average relative volatility.

Procedure

1. Prepare a calibration chart of refractive index (RI) vs. mole fractions of components A and B. 2. Fill approximately 2/3rd volume of the distillation ask with a mixture of A and B . 3. Start water circulation through the condenser. 4. Close the bottom sample "draw out" cock to prevent the overow of liquid through the sample line during the experiment. Open the top sample "draw out" cock to allow the air to escape when the heating is started. Switch on the heating mantle and allow the ask temperature to rise. 5. When the vapours rise to the top of the column, close the top "draw out" cock and increase the heating rate if necessary. After about 30 min, note the top and the bottom temperatures. If some milky liquid appears near the top "draw out" or the sample line, drain it in a small conical ask and discard. This could be due to the formation of emulsion of the organic liquid with moisture. 6. When the top and the bottom temperatures become steady (based on two successive readings taken at 10 min time interval) it indicates that the system has attained steady state and the samples may be withdrawn. 7. 2 to 4 ml of top sample is collected in a test-tube after purging o some quantity. The test-tube should be immediately closed to avoid losses. Determine the RI of the sample. 8. Count the number of actual plates in the column.

56

Figure 12.1: Schematic of the setup

57

Apparatus Observations

Data from the literature

**1. Moelcular weights of A and B . 2. Refractive indices of A and B at ambient temperature. 3. Densities of A and B at ambient temperature.
**

Calibration data for mole fraction vs. RI

S.N. Mole fraction of A

RI

Observations

1. Number of actual stages in the column. 2. Top temperature(◦ C) 3. Bottom temperature (◦ C) 4. RI of top and bottom samples 5. Mole fraction of top sample (XD ) 6. Mole fraction of residue (XB )

Calculations

1. Calculate the number of stages (theoretical) by McCabe Thiele method and calculate the overall eciency by equation 12.1. 2. Calculate the number of stages by Enthalpy-Composition method and calculate the eciency by equation 12.1. 3. Calculate the number of stages by Fenske's equation (equations 12.2 and 12.3 and calculate the eciency by equation 12.1. 4. Calculate number of transfer units (NTU) for a packed column.

yD

NTU =

yB

y∗

dy −y

5. Comment on the precaution and the sources of error.

58

Study hydrodynamic characteristics of packed columns. usually. Tower height is determined by packing characteristics. Estimate mass transfer coecient for absorption of ammonia into water.1 shows the experimental apparatus. Examine the gas and liquid connections made to the columns. which is connected to the computer (note that there is no read out for the transmitter). Determine ooding characteristics of columns with three dierent packing. Each column is packed with a dierent packing (Raschig Rings. 2. the height is found from mass transfer characteristics of the packing and the gas-liquid system. the pressure drop rises rapidly with gas ow and the liquid hold up in the column also rises.13 Gas-Liquid Absorption Objectives 1. namely. Eventually. mass transfer coefcient of the gas-liquid system and extent of separation. countercurrent gas-liquid contactors in which gas ows upward and liquid downward. Up to the loading point.a typical feature of turbulent ow. The columns are. Air and ammonia ows are adjusted with rotameters. The gas ow is usually turbulent and in a dry column. The diameter is determined from ooding characteristics of the column and. less than 5% ammonia).0 .8 to 2. the columns are lled with packing. Experimental Set-up Figure 13. say 60%. Design of the column involves estimation of diameter of the column and height of the packing required for specied separation. Theory Packed columns are used in chemical industry to absorb a gas from a mixture of gases or strip a volatile substance from a liquid. interfacial area. each of 5 cm internal diameter and one meter packed height. The pressure drop across the column is recorded with a dierential pressure transmitter. the pressure drop rises with gas ow with an exponent of 1. the pressure drop rises drastically and the liquid may splash back from the column. Pall rings and Intalox saddles). the pressure drop follows the same relation as in dry run. 59 . The temperature of the column is obtained with an RTD connected to the computer. It consists of three glass columns. The dissolved ammonia gas concentration is measured by Ion Selective Electrode instrument for ammonia. at the ooding point. the two streams are mixed to produce a mixture of specied concentration (work with dilute concentrations. Liquid ow is manipulated with a peristaltic pump. The pressure drop rises with an increasing ow of liquid because liquid lls up the column and the space for gas ow is reduced. Gas and liquid should ow through only one column at a time. Refer to Cussler (1984) for derivation of governing equation for tower height. To provide large interfacial area for mass transfer between gas and liquid. Flooding depends on pressure drop across the column. 3. The gas velocity corresponding to the ooding point is called ooding velocity and the column is operated at some fraction of this velocity. Beyond the loading point. it being higher at the bottom and lower at the top to allow the gas to ow upward. which can be controlled by a computer.

1: Experimental Apparatus for studying hydrodynamics of a packed column and ammonia absorption 60 .Figure 13.

Record the pressure drop for all air ows. Set air ow at 10 LPM and work your way up by raising it in increments of 10 LPM. description of experimental apparatus. raw data and analysis of ooding and mass transfer. Report It should include objectives.5 . Then. raise the gas ow slowly in increments of 10 LPM and record pressure drops.Procedure Flooding First. allow liquid to ow into the column and measure the pressure drop for increasing ow rates of gas.5 LPM. nd HTU and then mass transfer coecient for air/ammonia mixture and water system. Mass transfer The packed height of the columns is one meter. Use ve dierent liquid ows starting from about 1. Use mass balance to estimate gas phase concentration of ammonia in the outlet. study dry-run pressure drop by owing only air through one of the columns. For each liquid ow. From the equation given below. 61 . Repeat the above procedure for the other two packings.

There are various methods of determination of thermal conductivity suitable for dierent materials. 62 . Ti = surface temperature of the inner sphere. These reading in turn enable to nd out the thermal conductivity of the insulating powder packed between two shells. Applying Fourier Law of heat conduction for thin spherical layer of radius r and thickness dr with temperature dierence dT . Let ri = radius of inner sphere in meters.2) From the experimental values of q . the thermal resistance of both the surfaces is neglected. can be determined as. the heat transfer rate. ro = radius of outer sphere in meters. We assume the insulating powder as an isotropic material and the value of the thermal conductivity to be constant. Physical meaning of the thermal conductivity is how quickly heat passes through a given material. and Q = heat transfer rate (W). The power supply to heating coil is adjusted by using a dimmerstat and is measured by voltmeter and ammeter. One dimensional heat conduction in the radial is assumed across the powder layer and thermal conductivity can be determined as above under steady state conditions. Theory Consider the transfer of heat by conduction through the wall of a hollow sphere formed by insulating powdered layer packed between two thin copper spheres.14 Thermal Conductivity of Insulating Powder Introduction Thermal conductivity is one of the important properties of the materials and its knowledge is required for analyzing heat conduction problems. The insulating powder is packed between the two shells. The present apparatus is suitable for nding out thermal conductivity of materials in the powdered form. which is highly conductive. Thermocouples are used to measure the temperatures (Ti and To ). Q = −K 4πr2 dT dr (14. Separating variables. q dr = −dT 4πK r2 Integrating from ri to ro and Ti and To q= 4πkri ro (Ti − To ) ri − ro (14. Ti and To the unknown thermal conductivity K .1) where K = thermal conductivity (W/m◦ C). Ammeter readings are recorded.3) 4πri ro (Ti − To ) Apparatus and Specications The apparatus consists of two thin walled concentric copper spheres. Under steady state conditions the temperatures are noted and also the Voltmeter. ◦ C To = surface temperature of the outer sphere. The inner surface houses the heating coil. q(ro − ri ) K= (14. Thus the determination of this property is of considerable engineering importance. ◦ C Being a thin surface and copper.

ro = 100 mm Voltmeter . (a) (b) (c) (d) (e) Voltmeter reading (V ) = Volts Ammeter reading (I ) = Amps. 3. q = V I Watts The observations and results are tabulated and repeated for dierent wattages. Experimental Procedure 1.0 to 200 volts Ammeter .strip heating element Sandwiched between mica sheets. Temperature Indicator .0 to 300 ◦ C Dimmerstat 0 to 2 A . 4. 63 . 0 to 230 V Heater Coil. Note down the readings in the observation table as given below. Wait till a satisfactory steady state condition is reached. ri = 50 mm Radius of the outer copper sphere. Make the necessary electrical connections and give AC input to supply mains. Heat transfer rate. from 20 to 200 volts. Keep the heat input constant through out the experiment at various values by adjusting the dimmerstat.Specications Radius of the inner copper sphere. Heater Input (V I ) = Watts Temperature of Inner sphere Ti = ◦ C Temperature of outer sphere To = ◦ C 5. 2.0 to 2 Amps.

cp = specic heat. Notation: L = length.2) where hr = radiation heat transfer coecient hr = qr = A(Ts − Ta ) 4 s σ(Ts 4 − Ta ) Ts − Ta (15. equation 15. Gr = (L3 ρ2 gβδT )/µ2 = Grasho number.15 Heat Transfer by Combined Natural Convection and Radiation Theory In many engineering problems a surface losses or receives thermal energy simultaneously by convection and radiation. K = conductivity.1 can also be written as q = (hc + hr )(Ts − Ta ) A where qc . For Rayleigh Number between 104 and 109 . when a hot body is exposed to its surroundings at a lower temperature. The total rate of heat transfer is the same of the heat transfer rates by convection and radiation as given by 4 4 q = qc + qr = hc A(Ts − Ta ) + Aσ(Ts − Ta ) (15.3) Heat Transfer COecient for Natural Convection The heat transfer coecient for natural convection on vertical planes and cylinders is given by Nu = hc L = c[Gr P r]n = C(Ra)n K (15. β = 1/T for gases (T is in K).25 K (15. µ = viscosity. Ra = GrP r = Raleigh number. For example.5) 64 . P r = Cp µ/L = Prandtl number. ρ = density. α = coecient of thermal expansion.4) where N u = hc L/K = Nusselt number.P r]0. it loses heat both by convection and radiation and the two mechanisms of heat transfer act in parallel.1) = heat transfer rates by convection and radiation A = heat transfer area of the body.4 is given by Nu = hc L = 0.59[Gr. = average convection heat transfer coecient either natural convection hc or forced convection or both depending on the prevailing conditions = Surface temperature of the body Ts Ta = Ambient temperature = emissivity of the surface s σ = Stefan-Boltzman constant of radiation Equation 15. qr (15.

should be evaluated at the lm temperature.28 kg Specic Heat (Brass) 0. Ambient Temperature. nd out the slope at the required temperature. Support the heated cylinder on a wooden stand with the help of three glass rods. Knowing natural convective heat transfer coecient from Eq.5.683 .02624 0. W = 1.8826 1. The lm temperature is dened as Tf = Ts + Ta 2 (15. and calculate total heat loss from equation 15. cp = specic heat of the body.03365 0.2. t = time in s.1 cm.03003 0.075 400 0. Calculations Plot temperature versus time graph.091 kcal /kg C Ambient Air temperature Ta = Room Temperature 65 K 0.0090 2.484 Metal brass cylinder. 15.689 0.5 the rate of heat transfer due to radiation and radiation heat transfer coecient hr can be calculated from Eq. 15. the total rate of heat loss as given by eq. the temperature outside the boundary layer ). From knowledge of hr . 15.697 0.0057 1. the emissivity of the surface s can be calculated from eq. start recording the temperature at intervals of 5 minutes till the surface temperature reaches about 100◦ C. 15. Heat the metallic cylinder to about 350◦ C.65 cm. As soon as the temperature falls to 300◦ C.7. 15.6) where Ts = Surface temperature. Data Physical properties of Air at 1 atm pressure T (K) ρ (kg/m3 cp (kJ/kg◦ C 105 (kg/m s) 300 1.1774 1.0140 2.7 is equal to eqs.2.e. H =7. Total Heat Transfer When a body is heated to a certain temperature and allowed to cool. Under the condition of Natural Convection and radiation.7) where m = mass of the body in kg.3.0207 2. Experiemtnal Procedure Determine the mass of the cylinder and its surface area of for heat transfer. then the rate of heat transfer (or loss) to the surroundings at any time can be written as q = mcp dT dθ (15. D = 5.8462 350 0.03787 Pr 0. Perform the calculation as a function of temperature between 100 to 300◦ C.7833 1.1 & 15. T = temperature in K. Ta = Free stream temperature (i. 15.286 450 0.708 0.9980 1.The physical properties of the uid to be used in eq.

These occur at nucleating points or cavities in the surface. etc. refrigeration. evaporation takes place at small temperature dierences and with no bubble formation. The locally warmed liquid expands and convection currents carry it to the liquid vapor interface where evaporation takes place. 66 . an appreciable pressure dierence exists. NUCLEATE BOILING: As the surface becomes hotter. e. and is insignicant when the bubble is large.g. The nature and the rate of this heat transfer changes considerably as the temperature dierence between the metal surface and the liquid is increased. CONVECTIVE BOILING: When the heating surface temperature is slightly hotter than the saturation temperature of the liquid. 3. The pressure dierence increases as the diameter of the bubble decreases. When this happens there is considerable reduction in heat transfer rate and if the heat input to the metal is not immediately reduced to match the lower ability of the surface to transfer heat. BOILING: When a liquid at saturation temperature is in contact with the surface of a solid (usually metal) at a higher temperature. 4. THEORY 1. which form the nucleus for the formation of a bubble. The formation of bubbles normally associated with boiling is inuenced by the foregoing. heat transmission. and thermal equilibrium is restored. is equal to energy input. However. Thus in this mode. thermal and nuclear power generation in steam plants. the vapor inside a bubble must be at a higher pressure than the surrounding liquid. rening. and in practical applications the boiling is nearly always in this mode. the metal temperature will rise until radiation from the surface plus the limited lm boiling heat transfer. Exceptionally high heat transfer rates and heat transfer coecients with moderate temperature dierences occur in nucleate boiling. (This will be close to the saturation temperature corresponding with the pressure at the free liquid vapor interface). heat is transferred to the liquid and a phase change (evaporation) of some of the liquid occurs. 2. As soon as a bubble is formed. it expands rapidly as the warmed liquid evaporates into it. The buoyancy detaches the bubble from the surface and another starts to form. the excess vapor pressure is unlikely to produce bubbles.16 Boiling and Condensation Studies INTRODUCTION Boiling and condensation are vital links in the transfer of heat from hot to cold regions in countless applications. The pressure inside the bubble is the vapor pressure corresponding with the saturation temperature. Thus when no bubbles exist (or are very small) it is possible for the liquid temperature in the region of the heat transfer surface to be well above the temperature of the bulk of the liquid. the production of vapor bubbles is a very interesting and complex process. Although "boiling" is a common process. when the bubble is minute. Nucleate boiling is characterized by vigorous bubble formation and turbulence. FILM BOILING: Above the critical surface -liquid temperature dierence it is found that the heating surface becomes "Vapor locked" and the liquid is unable to wet the surface. Due to surface tension. the excess of vapor pressure over local liquid pressure increases and eventually bubbles are formed.

The chamber houses the heating element and the condenser. The condenser with 9 coils nickel plated copper tube if mean surface area approximately 0. a combustion process. a similar failure can occur. Voltmeter and Ammeter to measure electrical input to the heating element. with nickel plated brass end plates. 5.18 KJ kg−1 K−1 1 bar = 105 Nm−2 = 100 KNm−2 The panel consists the chamber with thick walled glass cylinder (80 mm bore × 300 mm long). If the source is radiant energy from.0015 m3 Specic Heat capacity of water = 4. Single Point Digital temperature indicator with 10◦ C resolution indicates the 67 .If the energy input is in the form of work (including electrical energy) there is no limit to the temperature which can rise until a failure or a "burnt out" occurs.0013 m2 (including area of end) Condenser surface area = 0. for example. The heating element with 300 Watt "High watt density cartridge heater swaged into a thick walled copper sleeve to give a uniform surface temperature.032 m2 .032 m2 Maximum permitted surface Temperature = 220◦ C Heater Cut-out Temperature = 170◦ C Fluid: RII Trichloro-uoromethane CCl3 F (NO OTHER FLUID SHOULD BE USED) Quantity of uid: (Liquid level to be not less than 50 mm above heating element) Approximately 0.8 WK−1 Dimensions of glass chamber: Nominal diameter = 80 mm Length = 300 mm Volume = 0.5 mm Diameter = 12. it may be possible to promote "dropwise" condensation.7 mm Surface area = 0. When lmwise condensation occurs. Besides the chamber. CONDENSING HEAT TRANSFER: Condensing of a vapor onto a cold surface may be "lmwise" or "dropwise". Immersion heaters must obviously design with sucient area so that the heat ux never exceeds the critical value. By treating a surface with a suitable compound. When this occurs the surface is not wetted by the liquid and the surface becomes covered with the beads of liquid which coalesce to form drops which then fall away leaving the surface bare for a repetition of the action. and many tube failures in the radiant action of advanced boilers are attributed to this cause.55 L Heat Transfer to surroundings from the chamber = 0. the surface is completely wetted by the condensate and condensation is onto the outer layer of the liquid lm the heat passing through the lm and into the surface largely by conduction. Heat transfer coecients with dropwise condensation are higher than with lmwise owing to the absence of the liquid lm. Eective heating surface area is approximately 13 cm2 . SPECIFICATIONS AND EXPERIMENTAL SETUP Dimensions of the heating surface Eective length = 29. ranges 0 to 250 volts and 0 to 3 A respectively and Variable Transformer to give innitely variable heat input to the heating element. Charging and Drain valve tted to lower end plate-to charge or discharge R11. The consequence of a "burn out" in a nuclear power plant will be readily appreciated.

There is a long glass thermometer (0 to 50◦ C and 150 mm) to measure (i) Water inlet and outlet temperatures (ii) R11 liquid temperature and (iii) R11 vapor temperature. Glass thermometers are also mounted inside the glass cylinder to indicate the temperature of Rll liquid and vapor. The temperature of the copper sleeve is measured by a thermocouple and digital indicator. On the right side of the panel. the temperature dierences between the liquid and the metal being still quite moderate (200K). Nucleate Boiling will soon start and will increase until vigorous boiling is seen. This coil condenses the Rll vapor produced by the heat input and the liquid formed returns to the bottom of the cylinder for re-evaporation. indicating that evaporation is proceeding although at a low rate. The electric input to the heater may be varied from 0 to approximately 300 watts by a variable transformer. Increase the wattage in increments. OBSERVATIONS AND RESULTS Visual Demonstration of Convective. pressure Gauge ranging from -100 to +250 KN m−2 gauge to indicate pressure in chamber. DESCRIPTION OF EXPERIMENTAL SETUP A high "Watt density" electric heating element in a copper sleeve submerged in Rll liquid is mounted horizontally in a vertical glass cylinder. Water ow meter. The rate of evaporation falls to a low level and the water ow rate must be reduced to maintain a steady pressure. enables the rate of heat transfer at the condenser to be measured. The electrical input should be now reduced to about 60 watts. DEMONSTRATION OF FILMWISE CONDENSATION AND MEASUREMENT OF OVERALL HEAT TRANSFER COEFFICIENT The lmwise condensation which occurs with Rll can be clearly seen. Convection currents will be observed. At the upper end of the cylinder is nickel plated coil of a copper tube through which cooling water ows. Observe this and the liquid temperature at frequent intervals. It will be found that as the metal-liquid temperature dierence falls to about 40 K the boiling suddenly becomes vigorous as lm boiling reverts to nucleate boiling. Increase the power input and at between 200 and 300 watts the nature of the boiling will be seen to change dramatically and at the same time the metal and liquid temperature dierence rise quickly. keeping the vapor pressure at any desired constant value by adjusting the cooling water ow rate.temperature of the surface of the heating element. Allow the digital thermometer to stabilize. and at the same time liquid will be seen to collect and drip on the condenser coils. A controller incorporated in the temperature indicator switches o electric input if the temperature of the heating surface exceeds a pre-set value. and the resistance oered by the liquid is readily appreciated. The electrical power input should be now reduced to zero. Carefully watch the liquid surroundings the heater. On the left corner of the panel. The overall heat transfer coecient between the condensing vapor 68 . the actual heat transfer rate being obtained from the product of the Voltmeter and Ammeter readings. tapered glass tube with stainless steel oat and control valves. Careful examination of the heater surface will show that it is now enveloped in an almost unbroken lm of vapor and this is the cause of the reduced heat transfer rate. A cooling water ow meter used in conjunction with glass thermometers measuring the cooling water temperature. range 0 to 50. Nucleate and Film Boiling (Three Modes of Boiling) Turn on the electrical and water supplies and adjust both to low settings.

m λ = latent heat of condensation. note the water ow rate (mw). Tf = (Ts + Tw )/2 Where Ts = Saturation temperature. and the length of tube in 69 . To ) and the saturation temperature of Rll (Ts ).51Re−1/3 k 3 ρ2 g (16. φm = φ1 − φ2 ln φ1 φ2 (16.8) The condenser coil may be approximated as a stack of horizontal tubes. ESTIMATION OF CONDENSATION COEFFICIENTS For the horizontal tube. condensation coecients is given by Co = h( µ2 1/3 ) = 1. CALCULATIONS Heat transfer rate of cooling coil.4) (16.725( Do = tube diameter. h = 0. Tw = wall temperature The condensation coecient for a horizontal tube can also be estimated by.6) φ1 = Ts − Ti φ2 = Ts − To Overall heat transfer coecient U= Qw Aφm Where A = surface area of the condenser. When conditions are stable.5) (16. water inlet and outlet temperatures (Ti . m/L m = total condensate ow rate. J/Kg ∆t = Ts − Tw k 3 ρ2 gλ 1/4 ) ∆Do µ (16.7) Co = Condensation number Re = Film Reynolds number k = Condensate loading per unit length of tube. Qw = Mw Cp (Ti − To ) (16.and water may be found as follows: Adjust the voltage and the water ow rate until the desired pressure and condensing rate is established.1) (16.3) (16. Voltage (E ) and Current (I ). Kg/s L = length of the tube.2) Heat transfer rate from heater Qe = E × I Heat transfer to surroundings (by dierence) = Qe − Qw Log mean temperature dierence. m The physical properties should be evaluated at lm temperature.

then. of tubes in a stack.11) h1 = condensate coecient for the top tube in stack. n. i.9) nπDe Qw λ m= λ = latent heat of condensation..12) Overall coecient for a coil can be estimated from eq.5 hi = lm coecient for a straight pipe die = tube diameter De = Coil diameter die )hi De (16. There are. m Γ= (16. The estimated and the experimental coecients can be compared. (9) and (10) and taking into account the thermal resistance of the tube. other saturation temperatures and other condensation heat uxes. (16. say. N = No.e. 70 . The observations and results can be tabulated. This may be repeated at other water owrates. where De = Coil diameter. For a coil. rows of tubes. n turns.each horizontal row may be estimated as De. the inside lm coecient can be obtained as hi e = (1 + 3.10) Average condensation coecient for a stack of tubes is shown as hw = h1 −1/4 (16.

As the temperature of the tank liquid reaches to 700◦ C.p. Fix up the shaft of the propeller to the shaft of the fractional horse power motor and adjust the depth of the impeller from the bottom of the tank. 2. Equipment An insulated cylindrical vessel. 6. 4. Start the agitator and set its speed to a fairly high value. Follow the same procedure for at least three more dierent ow rates of the coil liquid in turbulent ow (say 7Kg/min. a variac to control the speed of the motor. 5. such that the depth is equal to 1/3rd of the tank diameter. by means of cooling water. say 1000 r.17 Heat Transfer Through a Submerged Helical Coil in an Agitated Vessel (Under Unsteady-State Conditions) Aim To evaluate overall and individual lm heat transfer coecients for cooling hot liquids in a stirred vessel. . propeller type impeller. Stop heating the liquid and let the temperature of the hot vessel liquid fall gradually. So as to give complete mixing and hence uniform temperature inside the tank. Heat the vessel liquid by means of an immersion heater to about 800◦ C and then keep the heater on. Charge the tank with appropriate amount of given liquid so as to make the depth of the liquid equal to the diameter of the vessel.m. owing through the helical coil submerged in the vessel. 10Kg/min) 71 . Continue recording till the temperature dierence between the vessel liquid and the outgoing coil liquid drops down to 450◦ C. helical coil. bucket and a balance. driven by fractional horse power motor. admit cold water through the helical coil and adjust its ow rate to a desired value such that the Reynolds number is greater than 104 (say 5Kg per minute). Clean the tank and the copper helical coil with ne emery paper and place the helical coil inside the tank on a wooden support. start recording the temperature of the tank liquid and outgoing liquid as a function of time. thermometers. immersion heater. Procedure 1. 3. 7. stop watch.

The equation 17. rph.dθ. where MC is the mass of the liquid inside the coil.dθ = WC Cpc (Tc − Tca )dθ (17. Mh = mass of hot liquid in the vessel.2 becomes U0 A0 ∆Tlm .dθ (17. θ Tca = temperature of incoming coil liquid at zero time. N = speed of the agitation.1) dtc 2 and U0 A0 ∆Tlm . Therefore.c (Tc ?Tca ) Kcal.1 reduces to − Mh Cph dth = U0 A0 ∆Tlm .dθ + dqs (17.4 U0 A0 Tc − Tca = WC Cpc (Tc − Tca )dθ ln(Th − Tca )/(Th − Tc ) 72 .2.2) If the vessel is properly insulated. Kcal. Heat transfer through the wall of the helical coil during the interval dθ = U0 A0 ∆Tlm . due to temperature drop dTh is given by −Mh Cp.Observations Time (θ min) Th ◦ C Tc ◦ C Tca ◦ C 0 70 Th = temperature of vessel liquid at any time. Kg/hr. W = ow rate of cold water in the coil. − Mh Cp. Kg.3) Since during the small interval . Theory Heat lost by the vessel liquid during small interval of time dθ. Accumulation of heat inside the coil during the interval (dθ) = MC Cpc dtc /2. the heat loss to the surroundings is negligible and consequently equation 17. the accumulation or depletion of heat inside the coil is inappreciable compared to the amount of the heat carried away by the coil liquid. the term MC Cpc dtc /2 can be dropped from the equation 17.h dth .4) From the equation 17. Heat lost from the vessel liquid to the surrounding during the interval dθ is dqs . θ Tc = temperature of outgoing coil liquid at any time. Heat carried away by the coil liquid during the small interval.dθ = WC Cpc (Tc − Tca )dθ + MC Cpc (17.h dth = U0 A0 ∆Tlm . dθ is equal to (Wc dq)Cp.

or

ln

U0 A0 (Th − Tca ) = (Th − Tc ) Wc Cpc

(17.5) (17.6)

or or (Th − Tca )/K = Th − Tc .

U 0 A0 (Th − Tca ) = e Wc Cpc = K(say) (Th − Tc )

Tc = Th −

1 Th Tca + = Th 1 − K K K

+

Tca K

(17.7)

Method of Calculation

Method 1

Make a plot of Tc against Th and calculate the slope of the graph by the method of least squares. From the calculated slope, nd out the value of K . Knowing the value of K , calculate U0 from equation 17.6. This method of calculating U0 is valid only when Tca (incoming coil liquid temperature at zero time) is constant.

Method 2

When Tca is also a variable, nd the average value of K for all readings by using equation 17.6 and then calculate U0 from the same equation using the average value of K .

Method 3

**From equation 17.3 and 17.4
**

− Mh Cph dth = WC Cpc (Tc − Tca )dθ −Mh Cph dth = WC Cpc Th 1 − 1 K + Tca 1 − Tca dθ = WC Cpc 1 − K K 1− 1 K

θ

(17.8)

(Th − Tca )dθ

or

−

Th Thi

WC Cpc dTh = Th − Tca Mh Cph

dθ

0

**Assuming Tca to be constant,
**

ln WC Cpc Thi − Tca = Th − Tca Mh Cph 1− 1 K θ

(17.9)

where Thi = temperature of vessel liquid at θ =0 If we plot ln(Thi − Tca )/(Th − Tca ) against θ , we will get a straight line passing through the origin. Calculate the slope by the method of least squares and from the slope nd out the value of K . Use this value of K to evaluate U0 from equation 17.6

73

Method 4

From equation 17.3

Th

=

Thi

U0 A0 Mh Cph

θ

=

0

U0 A0 θ Mh Cph

(17.10)

Plot 1/?Tlm against Th and evaluate the area under the curve for dierent values of θ (or Th ). From the area calculate U0 by equation 17.10 for dierent values of θ. Calculate the mean value of U0 for the duration of run.

Calculation of HIC

Inside lm heat transfer coecient hi , for turbulent ow inside straight circular tube is given by the Sieder and Tate equation:

1/3 Straight tubehi = 0.023 Re0.8 P rb b

K di

µb µw

0.14

(17.11)

Inside coil lm heat transfer coecient hic , for turbulent ow inside the helical coil is given by the following equation: d Straight tube: hic = 1 + 3.5 i hi (17.12)

Dc

**Where, di = inside tube diameter, Dc = Helix diameter
**

Calculation of Hoc

Coil outside lm heat transfer coecient, hoc , can be calculated by subtracting metal wall resistance as well as inside coil lm resistance from the overall resistance, neglecting the dirt lm resistance.

1 1 1 X = + + U0 A0 hoc A0 hic Ai Km Am 1 d0 1 d0 X 1 = + + U0 hoc di hic dm Km 1 d0 1 d0 X 1 = − − hoc U0 di hic dm Km 1 hoc = 1 d0 1 d0 X U0 − di hic − dm Km

(17.13) (17.14) (17.15) (17.16)

where Km = thermal conductivity of the tube wall, dm = mean diameter of the coil tube.

**Observations and Specications
**

Data:n = 11, d0 = 1.27×10−2 m; Dc = 24 cm; H = Dt = 30×10−2 m; Cpc = 0.998 Kcal/(kg◦ C) 74

Cph = 0.466 Kcal/(kg◦ C) A0 = πd0 × πDc × n = π 1.27×10−2 × π 30×10−2 × 11 = 0.3480 m2 . mass of oil = Mh = πD2 /4 × H × ρoil = = π(30)2 /4 × 30 × 0.86 = 18.25 Kg.

Oil Used: - SERVOTHERM medium oil (Essotherm 500 or hytherm 500 oil) Flow rate of water = 4.0 Kg/min = 240 Kg/hr Th = temperature of oil in vessel in ◦ C Tca = inlet temperature of cold water in ◦ C Tc = outlet temperature of cold water in ◦ C

Specimen Calculations

Method I

Tca 1 )+ {from y = mx + c} K K

Tc = Th (1 −

(17.17)

Th = temperature of vessel liquid at any time, Tc = temperature of outgoing cooling uid, Tca = temperature of incoming cooling uid. K is determined as follows: Calculate slope using least square method. If Tc is plotted against Th then

Slope = m =

XY 2 Si

1 1 1 1 Now, Si2 = n−1 [ n Xi2 − n ( 1,n Xi )2 ]SX Y = n−1 [ n Xi Yi − n ( n Xi )( n Yi )] where n is number 1 1 1 1 of readings Calculation for ow rate of 4.0 kg/min i.e. 240 kg/hr Th2 = Xi = 1054; Tc = Yi = 684; X( i2 ) = 54510 1 1 1 Therefore S = 20 [54510 − 20 (1054)2 ] = 80.46 Xi Yi = 34599.75; therefore SX Y = 20 [34599.75 − 1 21 (1054)(684)] = 13.47

Slope m =

U0 =

P

XY 2 Si

=

13.47 80.46

1 = 0.167 = (1 − K ) therefore K = 1.2

Wc Cp clnK A0

= 3.388

kcal ◦ C min.m2 .

= 203

kcal hr.m2 .◦ C

Method II

**Not applicable, because Tca is not a variable in our experiment.
**

Method III

ln

Wc Cpc 1 Thi − Tca = (1 − ) Th − Tca Mh Cph K

θ

dθ

0

(17.18)

75

19) Therefore K = 1 slope∗Mh Cph 1− Wc Cpc a therefore let X = ln( tth i−tcca h −t slope for ow rate = 4 kg/min = 240 kg/hr θ= Xi = 210 Xi2 = 2870 2 Si = (210)2 1 [2870 − ] = 32 19 20 (17.21) SXY = 1 1 SXY 2.083 (17.47 kcal/ (kg ◦ C). then U0 is calculated.23) U0 = Wc Cpc kcal = 88.197Slope = 2 = = 0.26) A graph of 1/∆Tlm vs Th is plotted and area under the curve is determined for dierent intervals of Th .446 4∗. Mh = 18.998 = 1.6728∗18.86 − (210)(15.25) Th Thi dTh U0 A0 = ∆Tlm Mh Cph dθ = 0 U0 A0 θ Mh Cph (17.86 (17.65 A0 hr.5◦ C −Tca The graph of ln( Thi−Tca Vs θ. It may be noted that Ath = indicated area under the curve from Thi to Th .25∗0. A0 = 0.25)] = 2.20) Yi = ln( th i − tc a ) = 15. is a straight line passing through origin.3480 m2 76 . Cph = 0.22) K= = 1 1− 0.Tca = constant = 28.25 th − tc a Xi Yi = 201.m2 .06728 19 20 35 Si 1 1− slope∗Mh Cph Wc Cpc (17.25 kg. Slope = Wc Cpc 1 (1 − ) Mh Cph K (17. Flow rate 4 kg/min (240 kg/hr). Slope is calculated by the Th method of least squares.◦ C (17.197 [201.24) Method IV Tc − Tca ln Th −Tca Th −Tc θ ∆Tlm = (17.

14 (17. hi straight tube = 0.32) x = thickness of the tube = Tabulate the calculated results and comment about the results.27) where Ki = conductivity of the uid.m. do −di 2 = 1. dm = hO C U0 di hic dm Km ln d0 di kcal Km = mean thermal conductivity of the coil material (copper) = 333.72 hr.◦ C (17.8 P rb b 1/3 µb µw 0.527 Re = kcal hr.796 Aρ K To Calculate hOC 1 1 d0 1 d0 X do − di = −( ) − . For Helical Coil hic = 1 + 3.30) (17.29) (17.95 2 77 .023 K di Re0.Calculation of Heat Transfer Coecient For turbulent ow in a straight tube The following equation was given by Sieder & Tate.m2◦ C 4Wc d i vρ = > 104 (Turbulent ow) µ πdi µb v= 1 Cp µ 1 W Pr3 = ( ) 3 = 1.27−0.28) (17.31) Ki = 0.5 di Dc hi straight tube (17.

is in general. Apparatus The apparatus consists of 1. its ow rate and the curvature ration (di /Dc ). A turbine type agitator. speed and location of the stirrer. Procedure 1. Change the measured quantity of the. The outside coil lm heat transfer coecient. N = agitator speed r. 3. Fix the stirrer in the vessel in such a way that the depth of the agitator measured from the bottom of the tank is equal to 1/3rd the tank diameter. a function of the physical properties of the vessel liquid. incorporating all the variables under consideration. 3. are helpful in the design of units like isothermal batch or continuous ow stirred tank reactors. and auto transformer to control the speed of agitator. equipped with a helical coil.) . 2. Clean the copper helical coil with ne emery paper. Introduction Studies on heat transfer in stirred vessels. Da = agitator diameter. tachometer etc. A stirred vessel with a helical coil can also be used a heat exchanger for heating or cooling of process liquors. hoc Dt =C K 2 Da N ρ µ d Cp µ K e µ µw f where Dt = vessel diameter. connected to a fractional horse power motor. hoc .18 Heat Transfer Through Coiled Tubes in an Agitated Vessel (Under Steady-State Conditions) Aim Determination of coil side heat transfer coecient while transferring heat from an agitated liquid in a vessel to cold water owing through the coil. 4.p. Tc2 ) and jacket side hot water (Tj1 . For dimensionally similar systems. Tj2 ). the design. 2. 78 . coil liquid (Tc1 . dimensions. The inside coil lm heat transfer coecient. the geometry of the coil (di and Dc ) and details of construction (at bottom. hemispherical bottom etc.h. Stop watch. Precision thermometer to measure the temperature of hot vessel liquid (Th ). hic is a function of the physical properties of the coil liquid. A lagged. hoc is correlated in terms of dimensionless groups. size and condition (baed or unbaed) of vessel. at bottom cylindrical vessel with a helical coil. given liquid into the vessel so as to make the depth of the liquid equal to the diameter of the vessel. submerged in the vessel under steady state conditions.

10Kg/min). Calculation of hi and ho by Wilson's plot: plot the graph of 1/Uo vs 1/Vi0.p. 6.4. by measuring it with the tachometer.c (Tc2 − Tc1 ) = Uo Ao ∆Tlm Kcal/hr. ow rate of cold liquid and speed of agitator. 2. At the steady state.8 and nd out the intercept and slope of this graph. temperature of vessel liquid. Repeat the above procedure by changing the cold water ow rate for the range of 104 < Re < 105 . Keep the stirrer speed at 600 r. When vessel liquid is heated up to about 400◦ C admit the cold water through coil at the rate which will give Re = 104 (5Kg/min. Heat gained by coil liquid. note down. Admit the hot water into the jacket side and constant ow rate (6 to 7 kg/min) and temperature of 600◦ C. Calculations 1. 5. 7. where Ao = (πdo )(πdc n) m2 do = outer diameter of the coil tube dc = mean helix diameter n = number of turns of the coil ∆Tlm = (Th − Tc1 ) − (Th − Tc2 ) ln Th −Tc1 Th −Tc2 Calculate Uo . 8. inlet and outlet temperatures of coil liquid. qc = Wc Cp.m. 79 .

1) (19. Leva's correlation is given as follows. Platform scale balance. The packing is 3/8" × 3/8" raschig rings. Outer diameter of packed tube (Do ) = 60. Theory The presence of solid packing increase the wall heat transfer coecients in a packed bed several times over that in an empty tube at the same uid ow rate.6 mm. hiP Dt = 0. to those obtained by empty tube for the same ow rates.9 exp 0. Auxiliary piping and pumping equipment. Raschig Ring Dimensions: Length = 13. Inner diameter of jacket (Di ) jacket = 86 mm.7 cm length and rest on a perforated plate. lled inside the tube up to 45.60 (19.d.0 cm i. copper tube is tted with an external jacket. Data Inner diameter of packed tube (Di ) = 50 mm. Inner diameter = 7.2) hiP Dt = 0. Outer diameter = 13.75 −6dp Dt For dp/dt < 0. hip .6 mm. The packed bed exchanger is equipped with thermometers to measure the inlet and outlet temperatures of cold water and hot water owing respectively on the tube side and jacket side. Leva has correlated xed bed heat transfer coecients over a wide range of variables. Weighing container and.19 Heat Transfer in a Packed Bed Aim To determine the wall heat transfer coecients in a packed bed and establish the relationship between Nusselt number and Reynolds number.6 mm. Experimental setup as specied.35 For 0.6 mm.2mm.813 k Dp G µ 0. Experiemtal Setup A 5. It is found that the ratio of the coecients in the packed bed to that in the empty pipe varies in the ratio of diameter of the packing to that of the tube.125 k Dp G µ Apparatus Hot water with constant inlet temperature as heating medium. 80 . (with 3 mm holes) having 45% hole area. Length of packed test section = 457. This turbulence tends to prevent the build up of a slow moving layer of uid next to the wall and also increases the radial heat transfer within the uid to the tube.35 < dp/dt < 0. further to compare the packed bed heat transfer coecients. An enhancement in the wall heat transfer coecient in a packed bed is due to the turbulence caused by higher local uid velocity inside the voids of the solid packing. Stop watch.

Admit hot water through the jacket at 60◦ C and at constant ow rate of about 10 kg/min. Observations Run Flow Rate of Inlet Temp of Outlet temp of Flow Rate of Inlet temp of Outlet temp of No.3) Ai = inside heat transfer area = πdi L m2 . Repeat the above procedure for several ow rates. Flow rate of cold water in the packed bed should be in the range of 2 to 7 kg/min for constant operating conditions of heating medium. kg/hr tc1 . 3. m L = length of test section. di = inner diameter of the tube. 5. Ws kg/hr. kg/hr th1 . Steam Temperature ts ◦ C. 81 . Determine the exact ow rates of cold water and hot uid by weighing the liquids collected in a known interval of time (the weight of the liquid collected in a container or bucket should be above 5 kg.Procedure 1. qh = wh cph (Th2 − Th1 ) kcal/hr. record the inlet and outlet temperatures of cold water and hot water. qh = qc (within 5 % error). m Calculate values of Ui for the several runs taken. qc = wc cpc (Tc2 − Tc1 ) kcal/hr Heat lost by hot water. qavg = Ui Ai ∆Tlm where ∆Tlm = (Th2 − Tc1 ) − (Th1 − Tc2 ) ln Th2 −Tc1 Th1 −Tc2 (19. Steam Condensate Rate. When the steady state is reached.◦ C tC2 . 2.◦ C th2 . cold Water cold water cold Water hot water hot water hot water Wc . 4.◦ C Wh . Admit the cold water through the packed tube and set its ow rate to the desired value as indicated by the calibrated Rota meter.◦ C 1 2 3 4 If Steam is used as Heating Medium: Steam Pressure . Method of Calculation Heat gained by cold water.

Estimation of hi for an Empty Tube Calculate the inside lm heat transfer coecient for the empty tube for each of the mass ow rates used. and if the ow is intermediate between laminar and turbulent ow regions.539 kcal/hr. from equation given below. For clean surfaces 1 1 X 1 = + + Ui Ai hO AO Km Am hi Ai Knowing h0 .4) Or. 1/U0 vs 1/Vi0. D2 = outer diameter of inner packed tube. Cph = 0.14 (19. (m/hr).9986 kcal/kg◦ C.8 Cp µ k 0. for turbulent ow ho De = 0. Vi = supercial uid velocity inside the packed bed. wall lm heat transfer coecient of a packed bed relative to that of an empty tube. depending upon the type of ow.14 De = equivalent diameter D1 − D2 (19. µ|35◦ C = 7. i Calculate NRe = Di uρ/µ and use the appropriate equation to calculate the inside lm heat transfer coecients in circular tubes.9978 kcal/kg◦ C. 2100 < NRe < 104 .e.14 When hot water is used as heating medium in the concentric annulus. Ui and metal wall resistance. 2. then using Wilson's plot.◦ C.m. viz.s 82 . Here Ai = πd2 /4 where di = inside diameter of the tube.8 to obtain h0 and hi . use Colburn's Jh factor charts. viz. Kwater = 0.Method . h0 can be estimated from the following equations: For laminar ow: W Cp ho De = 1.49 × 10−4 kg/m. Calculation of hi 1.5) 2 2 The hydraulic radius = 4× cross sectional area/wetted perimeter = (D1 − D2 )/(D1 + D2 ) = D1 − D2 Where D1 = inner diameter of inner packed tube. Compute the ratio of hip /hi i.023 k Dp ρ µ 0.75 k KL 1/3 µ µw 0. Calculate hi in a packed bed by Leva's correlations given in equations (1) and (2) and compare them with the experimental value obtained above by equation (8) Film Coecients for an Empty Tube If water ow inside the tube is fully developed turbulent ow. Use Colburn's Jh factor for the intermediate ow regimes.86Re1/3 P r1/3 k D L 1/3 µ µw 0.I Calculation of ho : For laminar ow ho De = 1. Tabulate the values of this ratio and plot them against NRep hip /hi vs dp e/u Useful data Cpc = 0. we can calculate hi from the above equation.

Results Conclusions 83 .

for nned tube heat exchanger and 30 min. of water through charging valve provided at the top of the steam generator and close it. Procedure 1. for bare pipe. 4. steam will start coming out of the needle valve. When the test section (nned tube heat exchanger) is fully heated up. Now regulate the needle valve in such a way that only condensate comes out of it. note down the volume of condensate collected and time interval. 3. 5. of switching on the heater. 4. gauge as per the requirement. If the quantity of condensate collected is same for 2 to 3 consecutive readings (within experimental accuracy). otherwise electrical heater will burn out. 84 . 6. Longitudinal n heat exchanger.20 Finned Tube Heat Exchanger Objective To determine the eciency of given longitudinal/pin n and compare it with the theoretical value for the given n. Steam generator to generate steam at constant pressure. Close the drain valve and charge 4 lit. Steam will start forming within about 15-20 min. IMPORTANT INSTRUCTIONS: Follow instructions 1 and 2 without fail. 2. 2. The pressure can be regulated between 0-1 atm. 3. The steam generator is also provided with temperature indicator and a dead weight safety valve. During this period. Open the drain valve provided at the bottom of steam generator and drain out the water from steam generator completely. Pin n heat exchanger. At this point of time also regulate the voltage supplied to the electrical heater so as to keep the pressure in the steam generator constant. Once the steam generation starts. Close the needle valve on condensate drain line simultaneously starting the stop-watch. Repeat the procedure given in 4 for pin n heat exchanger as well as bare pipe. keep open the valve to one of the test sections (either longitudinal n heat exchanger or pin n heat exchanger). Ensure that the dead weight safety valve is free. Initially supply full voltage to the electrical heater. Apparatus 1. Collect the condensate accumulated at an interval of 15 min. Also keep the needle valve at the end of test section open. Start the electrical heater of steam generator. drain out completely the condensate it any. Once the test section (nned tube heat exchanger along with bare pipe without ns) is fully heated. the nned tube heat exchanger will start getting heated up and condensate will start coming out of the needle valve provided at the bottom of condensate collector. Bare pipe without ns.

Ao =Inside and outside surface area [m2 ] When viscous liquids are heated in a double pipe heat exchanger or any standard tubular heat exchanger by condensing steam or hot uid of low viscosity.Theory In a heat exchanger. longitudinal ns and transverse ns. and longitudinal n eciency for this case is given by the expression: ηf in = tanh(mL) mL (20.005 times) compared to that for the liquid or condensing vapour on the other side.2) 85 . Spikes. Longitudinal ns are used when the direction of ow of the uid is parallel to the axis of tube and transverse ns are used when the direction of the ow of the uid is across the tube. pins. Finite heat dissipation from the tip. The outside are of a nned tube consists of two parts: the area of ns and the area of bare tube not covered by the bases of ns. Under this condition the rate of heat transfer will depend on the overall resistance to heat transfer given by the equation: 1 1 x 1 = + + Ui Ai hi Ai KAlm ho Ao (20. This condition even though cannot be realized in practice. hot and cold. Two types of ns. Ui = Overall heat transfer coecient based on inner area [Kcal/hr m2 ◦ C ] Uo = Overall heat transfer coecient based on outer area [Kcal/hr m2 ◦ C ] hi . 3. the heat transfer coecient of viscous uid or gas cannot be improved much. Since. are separated by a metal wall. the two uids namely. dt/dx is assumed to be zero at the tip. the lm heat transfer coecient of the viscous liquid will be much smaller than that on the hot uid side and will therefore.ho = Inside and outside lm heat transfer coecients [Kcal/hr m2 ◦ C ] Ai . are in common use viz. certain type of heat exchange surfaces. called extended surfaces. 2.1) where. but considering that the tip area is negligible as compared to the total n area. To conserve space and to reduce the cost of equipment in these cases. This condition is also present in case of air or gas heaters where the gas side lm heat transfer coecient will be very low (typically of the order of 0. Fin of innite length so that there is no heat dissipation from its tip. Insulated tip. Even though the assumption of insulated tip is invalid. 1. A unit area of n surface is not as ecient as a unit area of bare tube surface because of the added resistance to the heat ow by conduction through the n at its base. studs or spines are also used for either direction of ow. have been developed in which outside area of tube is increased many fold by ns and other appendages. The expression for n eciencies can be derived by solving the general dierential equation of heat conduction with suitable boundary conditions. Generally three boundary conditions are used.01 to 0. heat dissipated from tip can be neglected and hence. become controlling resistance for heat transfer. most of the ns are treated under this category. or in other words temperature at the tip of n is same as that of the surrounding uid. the only alternative is to increase the area available for heat transfer on that side so that its resistance to heat transfer can be reduced.

O. (20. If the n height L should be sucient (of the order of 5 to 8 cm). cm. or any gas in forced convection will be much higher than 20. Tube area available for heat transfer in nned tube heat exchanger: AB = (ΠD − N b)xw = m2 86 . and as the value of mL increases. the n eciency decreases. Width of n (W) 3. Thermal conductivity of n material (K) 2. The value of lm heat transfer coecient for any other liquid in natural convection. Bare Tube: 1. Thus. A reasonable value of n eciency will be around 50 to 75% for which mL should have a value between 1 and 2. O.D.= (hC/KA) h = lm heat transfer coecient from the n surface [Kcal/hrm2◦ C ] C = circumference of the n [m] K = thermal conductivity of n material [Kcal/hr m◦ C ] A = cross-sectional area of n [m2 ] From the above equation. ◦C Calculations 1. Length of tube (l) : 2. then it can be seen that the value of h should be around 10 to 20 which can be given by air in natural convection. the given set-up is used for heat transfer to air in natural convection region. it can be seen that the n eciency is a function of mL. Cross-sectional area of n (A): A = wxb = m2 3.6) 2. Thickness of n (b) 4. of n tube 6. Kcal/hr m◦ C cm. cm. 4 cm. Finned Tube: 1.4) (20. T : ambient : : : : : : cm.D. Height of n (L) 2. cm. Fin area available for heat transfer: AF = CxLxN = m2 4.3) (20. Number of ns (N) 5.5) (20. m where Observations 1. Circumference of n (C): C = 2(w + b) = m. of tube : 3.

5. Heat given out by steam through nned tube heat exchanger (Q1 ): Q1 = (m1 x)xλ = Kcal/hr (20.12) Conclusion 87 . ηf in (Theoretical) = tanh mL/mL 12. Amount of heat that can be dissipated by ideal n: Qideal = AF × h × ∆T = Kcal/hr (20. m = 10. Film heat transfer coecient from bare tube (h): h = Q2 /(Ax∆T ) = A = ΠDL = ∆T = (Tsteam − Tambient ) = Kcal/hrm2 C.10) 13.7) 6.9) where λ = latent heat of vaporization of water at steam pressure (Kcal/Kg) 8. Total area of nned tube heat exchanger: At = AF + AB = m2 (20.8) 7. Heat given out by steam through bare tube (Q2 ): Q2 = (m2 x)xλ = Kcal/hr (20. mL = (hC/KA) = 11. m2 .11) 14. Amount of heat actually dissipated by n: Qf in = Q1 − (AB × h × ∆T ) = Kcal/hr (20. ◦ ◦ C 9. Observed value of n eciency: η(Observed) = Qf in = Qideal (20.

(It is preferable to have 15 . Stainless steel double pipe heat exchanger with facility to measure inlet and outlet temperature of hot uid with accuracy of 0. 4.1◦ C. 4. and 5 amp. Initially run the pump at slow speed. An insulated stainless steel tank with bottom discharge to measure the ow rate of hot uid.3◦ C. Ensure that the valve at the bottom of measuring tank is open. The set point should be set around 65 to 70◦ C. This will ensure constant ow rate of cooling water through the heat exchanger). 88 . Note down the temperature dierence between inlet and outlet temperatures.21 Heat Transfer in Laminar Flow Objective To determine the overall heat transfer coecient making use of logarithmic mean temperature difference. Connect 15 amp. Procedure 1. Check the inlet and outlet temperatures of the uid indicated by digital themometer. Cold uid circulation pump with speed variation mechanism. (Digital thermometers can give errors upto 1◦ C which is generally very dicult to bring down). Open the valve on the outlet line of the hot uid tank.C. plug pins to stable 230 V A. From overall heat transfer coecient. switch (main switches). Bare pipe without ns. which gives zero error. 3. capacity container with bottom outlet connected to pump suction line and cold water supply falling freely in the container to keep water level in it at a constant height. The steam generator is also provided with temperature indicator and a dead weight safety valve. Connect the suction line of cold uid circulation pump to cold water supply line. Care should be taken to connect these two pins in dierent phases of the power supply.30 lit. 2. Steam generator to generate steam at constant pressure. switch on the heater of the hot uid tank by switching on the D. Switch on the dual temperature indicator cum controller. Apparatus 1. electric supply. A stainless steel insulated tank with a heater. The inlet and outlet temperatures of cold uid is measured with liquid in glass thermometer of 1◦ C accuracy. 2. determine the individual lm heat transfer coecient and verify the Seider-Tate equation for laminar ow heat transfer. 5. Switch on the power supply to hot uid circulation pump and slowly increase the speed of the pump by regulating the voltage supplied to it by adjusting the regulator knob. After noting down the zero error in the digital thermometers. Hot uid circulation pump with speed variation mechanism. Keep this ow rate constant throughout the experiment. 3. Check the set point of the controller. Pin n heat exchanger. Adjust the cooling water ow rate through the heat exchanger such that its temperature rise is restricted to about 2 .P.

N u = 1. 7.c. At low Reynold's number (Re < 2100). in order to have laminar ow through the heat exchanger). Also note down the inlet and outlet temperatures of cooling water. As soon as the liquid level in measuring tank reaches the top mark. Adjust the ow rate of hot uid through the heat exchanger by adjusting the speed of hot uid circulation pump. open the ball valve at the bottom of the measuring tank in order to avoid the over ow of uid from the tank. one can write. then Sieder-Tate equation can be used to predict the inside lm heat transfer coecient. for heat exchanger. 6. then all the physical properties will remain nearly the same and equation (3) can be re-written as: N u = constant × (velocity)1/3 89 . that the heat transferred to and through the uid is essentially by conduction. When heat is transferred through resistances in series. Theory In a heat exchanger. 1 x 1 1 = + + Ui Ai hi Ai KAlm ho Ao OR Ai 1 1 ∆xAi = + + Ui hi KAlm ho Ao Once the heat exchanger material and its geometry is xed. heat is transferred from hot uid to cold uid through metal wall. Repeat step 5 & 6 for at least 6 dierent ow rates of hot uid. The actual value depends upon individual lm heat transfer coecient on either sides. the ow pattern is laminar and the uid ows in an ordered manner along generally parallel "Filament like" streams which do not mix. The wall temperature is always between local temperatures of the two uids. then the resistance by the outside lm will remain almost constant. If ow through inner tube is in the turbulent ow regime. Thus. then the metal wall resistance x/KAlm becomes constant. the total resistance to heat transfer is the sum of individual resistances in series. Measure the ow rate of hot uid by closing the valve at the bottom of measuring tank and noting down the time required for liquid level to rise between two marks. if the ow rate of cold uid is xed and its mean temperature does not dier much for dierent ow rates of hot uid. the overall heat transfer coecient will depend upon the value of inside lm heat transfer coecient alone. Thus. Note down the inlet and outlet temperatures indicated by digital thermometer on the control panel after steady state is reached.5. Generally resistance oered to heat transfer by the metal wall is negligible as compared to resistance oered by convection. Heat transfer through metal wall is always by conduction while on both sides of metal wall it is generally by convection. Similarly.86(Re)1/3 (P r)1/3 If the bulk mean temperature does not dier much for dierent ow rates. It follows that in this type of ow. which generally separates these two uids. (The minimum ow rate of hot uid should at least be 70 c./sec.

0 cm. Observation Table Obs. m2 ◦C c. 2. 2. 4.c. 3. 3. 1. 5.c. ◦ C Time reqd for hot uid level to rise inlet (T1 ) outlet (T2 ) inlet (t1 ) outlet (t2 ) between two marks (t) sec. 8. inside lm heat transfer coecient can be calculated which can be used to verify Sieder-Tate equation.Substituting equation (4) in equation (2). the graph of 1/Ui vs 1/u1/3 (which is known as Wilson plot) should be a straight line with a slope equal to constant1 and intercept equal to constant2 .20cms. 7. 90 . 1. 6.27 cm. 5. From this graph. 7. 2. Observations 1.◦ C Cold uid temp. 85cms. c.No. Hot uid temp. 6. one can write it as: 1 1 = constant1 1/3 + constant2 Ui u Thus. Inside diameter of inner tube (d1 ) Outside diameter of inner tube (d2 ) Inside diameter of outer tube (D1 ) Length of heat exchanger (L) Inner heat transfer area of heat exchanger (A) Zero error of hot uid digital thermometers Volume of measuring tank between bottom and middle mark (V1) Volume of measuring tank between bottom and upper mark (V2) = = = = = = = = 1. 4.

1/(V 1/3 ) 1/U No.A: Table of Calculated Results Obs. 1. 6. 6. 5. N u Reynold's No. 2. Prandtl number of hot uid at mean temperature: Pr = Cp µ = K 91 . B: Table of Calculated Results Obs. 2. Inside lm heat transfer Nusselt No. 7. 3.c. 4. Cross-sectional area of inner tube: S= π 2 d1 = 4 cm2 2./sec) Q (Kcal/hr) u (cm/sec) U (Kcal/hr m2◦ C) 1. 4. Volumetric ow rate Amount of heat Velocity of LMTD Overall heat transfer No. Inside heat transfer area of heat exchanger: A = πd1 L = cm2 3. 7. 3. of hot uid transferred hot uid ∆Tlm ◦ C coecient (c. 5. 2◦ C) coecient hi (Kcal/hr m Nu Re Calculations 1.

3. Reynold's number: Re = Plots 1. Volumetric ow rate of hot uid: V = : c.c. (This should be a straight line) 2. Plot the graph of 1/Ui vs 1/(u1/3 ) on linear scale./sec.Sample Calculation for Reading No.log scale. Logarithmic mean temperature dierence (LMTD): LM T D = (T1 − t1 ) − (T2 − t2 ) ln (T1 −t1 ) (T2 −t2 ) = ◦ C 5. Plot the graph of Nusselt number vs Graetz number on log . V1 ( or V2 ) = t 2. Amount of heat transferred: Q= (V × ρ × 3600) × Cp × (T1 − T2 ) = 1000 Kcal/hr 4. Overall heat transfer coecient: U= Q = A∆Tlm Kcal/hr m2◦ C or ho = 1/Intercept = Kcal/hr 6. Value of intercept or graph of f vs [1/(u1/3 )](1/ho ) = m2◦ C 7. Inside lm heat transfer coecient: hi = 1 [( Ui ) 1 = 1 − ( ho )] hi d i = K d1 uρ = µ Kcal/hr m2 ◦C 8. Nusselt's number: Nu = 9. 1. Velocity of hot uid through heat exchanger: u= V = ρ cm/sec. Results Conclusions 92 . Pass a straight line through this and nd its slope.

22 Heat Transfer in Turbulent Flow Aim To determine the overall heat transfer coecient making use of logarithmic mean temperature dierence.2) Or 1 1 ∆xAi Ai + = + Ui hi KAlm h0 A0 Once the heat exchanger material and its geometry is xed. 1 1 ∆x 1 + = + Ui Ai hi Ai KAlm h0 A0 (22. heat is transferred from hot uid to cold uid through metal wall which generally separates these two uids. one can write. although desirable. for heat exchanger. 000). 4. When heat is transferred through resistances in series. Thus. Similarly.1◦ C. Apparatus 1. this enhancement of lm heat transfer coecient is accompanied by much higher pressure drop which demands higher pumping power. 3. turbulent ow is usually restricted to uids of low viscosity. A stainless steel insulated tank with a heater.3) 93 . if the ow rate of cold uid is xed and its mean temperature does not dier much for dierent ow rates of hot uid.1) (22. then Ditturs-Boelter equation can be used to nd out inside lm heat transfer coecient. the overall heat transfer coecient will depend upon the value of inside lm heat transfer coecient alone. The wall temperature is always between local temperatures of the two uids. N u = 0. 2. However. then the resistance by the outside lm will remain almost constant. The actual value depends upon individual lm heat transfer coecient on either sides. An insulated stainless steel tank with bottom discharge to measure the ow rate of hot uid.023(Re)0. Cold uid circulation pump with speed variation mechanism. determine the individual lm heat transfer coecients and verify the Dittus-Boelter equation for turbulent ow heat transfer. Theory In a heat exchanger. Thus. If ow through inner tube is in the turbulent ow regime. the ordered ow pattern of laminar ow regime is replaced by randomly moving eddies thoroughly mixing the uid and greatly assisting heat transfer. Stainless steel double pipe heat exchanger with facility to measure inlet and outlet temperature of hot uid with accuracy of 0. From overall heat transfer coecient. The inlet and outlet temperatures of cold uid is measured with liquid in glass thermometer of 1◦ C accuracy. Thus. 5. Heat transfer through metal wall is always by conduction while on both sides of metal wall it is generally by convection. At higher Reynold's number (Re > 10. Generally resistance oered to heat transfer by the metal wall is negligible as compared to resistance oered by convection. the total resistance to heat transfer is the sum of individual resistances in series.8 (P r)n (22. then the metal wall resistance (∆x/KAlm ) becomes constant. Hot uid circulation pump with speed variation mechanism.

(It is preferable to have 15 . (The minimum ow rate of hot uid should at least be 40 cc/s. we get: 1 1 = constant1 0.controller. 94 . Procedure 1. Connect 15 amp and 5 amp plug pins to a stable 230 V A. to maintain Reynold's number above 10. Also note down the inlet and outlet temperatures of cooling water. Switch on the dual temperature indicator . Check the set point of the controller. Check the inlet and outlet temperatures of the uid indicated by digital thermometer. The set point should be set around 65 to 70◦ C.8 (which is known as Wilson plot) should be a straight line with a slope equal to constant1 and intercept equal to constant2 . 4. 3. open the ball valve at the bottom of the measuring tank in order to avoid the over ow of uid from the tank. Adjust the cooling water ow rate through the heat exchanger such that its temperature rise is restricted to about 3-4◦ C. Ensure that the valve at the bottom of measuring tank is open. switch on all the (three) heaters of the hot uid tank by switching on their respective main switches. After noting down the zero error in the digital thermometer. As soon as the liquid level in measuring tank reaches the top mark. capacity container with bottom outlet connected to pump suction line and cold water supply falling freely in the container to keep water level in it at a constant height. electric supply. 7. Measure the ow rate of hot uid by closing the valve at the bottom of measuring tank and noting down the time required for liquid level to rise between two marks. This will ensure constant ow rate of cooling water through the heat exchanger). Adjust the ow rate of hot uid through the heat exchanger by adjusting the speed of hot uid circulation pump. Note down the temperature dierence between inlet and outlet temperatures. Keep this ow rate constant throughout the experiment. Switch on the power supply to hot uid circulation pump and slowly increase the speed of the pump by regulating the voltage supplied to it.8 + constant2 Ui u Thus.8 (22. Open the valve on the outlet line of the hot uid tank. the graph of 1/Ui vs 1/u0.C. 6.If the bulk mean temperature does not dier much for dierent ow rates. Note down the inlet and outlet temperatures indicated by digital thermometer on the control panel after steady state is reached. Repeat step 5 & 6 for at least 6 dierent ow rates of hot uid. then all the physical properties will remain nearly the same and equation (3) can be re-written as: N u = constant × (velocity)0.4) (22. 2. Initially run the pump at slow speed. Connect the suction line of cold uid circulation pump to cold water supply line. inside lm heat transfer coecient can be calculated which can be used to verify Dittus-Boelter equation.30 lit. From this graph. 5.5) Substituting the above equation in equation (2). which gives zero error (Digital thermometers can give errors upto 1◦ C which is generally very dicult to bring down). Care should be taken to connect these two pins in dierent phases of the power supply.000 in the heat exchanger).

◦ C Cold uid temp. 95 . Hot uid temp. 2. cm. Outside diameter of inner tube (d2 ) = 3.c. cm3 . Volume of measuring tank between bottom and middle mark (V1 ) = 8. Volumetric ow rate of hot uid: V = V1 ( or V2 ) = t c. Calculations 1. 4./sec. Obs. ◦C cm. 3. Length of heat exchanger (L) = cm. cm. 7.Observations 1. Prandtl number of hot uid at mean temperature: Pr = Cp µ = K 1. Cross-sectional area of inner tube: S= π 2 d1 = 4 cm2 2. ◦ C Time reqd for hot uid level to rise inlet (T1 ) outlet (T2 ) inlet (t1 ) outlet (t2 ) between two marks (t) sec. m2 .No. 6. Inside diameter of inner tube (d1 ) = 2. Inner heat transfer area of heat exchanger (A) = 6. 5. Zero error of hot uid digital thermometers = 7. Inside heat transfer area of heat exchanger: A = πd1 L = cm2 3. Inside diameter of outer tube (D1 ) = 4. Volume of measuring tank between bottom and upper mark (V2 ) = Observation Table cm3 . 1. 5.

Velocity of hot uid through heat exchanger: u= V = ρ cm/sec. Nusselt's number: Nu = 9. (This should be a straight line). Reynold's number: Re = Plots Plot the graph of 1/Ui vs 1/u0. Amount of heat transferred: Q= (V × ρ × 3600) × Cp × (T1 − T2 ) = 1000 Kcal/hr 4. Logarithmic mean temperature dierence (LMTD): LM T D = (T1 − t2 ) − (T2 − t1 ) ln (T1 −t2 ) (T2 −t1 ) = ◦ C 5.2. 3. Overall heat transfer coecient: U= Q = A∆Tlm Kcal/hr m2◦ C or ho = 1/Intercept = Kcal/hr 6. Value of intercept or graph of f vs [1/(u1/3 )](1/ho ) = m2◦ C 7.8 on linear scale. Inside lm heat transfer coecient: hi = 1 [( Ui ) 1 = 1 − ( ho )] hi d i = K d1 uρ = µ Kcal/hr m2 ◦C 8. Conclusions 96 .

Observe the partially open centrifugal pump. valves and pumps 2. how the anged ends are tted together (do you need a gasket? why?).1: Schematic diagram of the piping network 1. Procedure Figure 23. ttings.) 2. To identify the dierent types of pipes. ttings. For example what are the types of impellers used? How are the open type and closed type impellers dierent? Where are the dierent impellers used and why? Which is the suction line and which is the discharge line? Is there a need to prime the pump? why? 97 . clockwise/anti-clockwise. To visualize the ow through valves and pumps and make sketches of the same 3. To measure the water ow rate through various sections of the piping network Theory The distribution of ow rates of a uid in piping network is related to the resistance oered by dierent segments of the network. Observe the display of pipes.23 Flow Through Piping Networks Objectives 1. the uid path through the dierent valves (how are globe and gate valves dierent? What are they used for? etc. To build a network using some of the above components 4. valves and pumps in the laboratory. For example note if the threads are on the outside/inside.

How ever make sure that the ow rate out of the source tap is the same as in the earlier step (How would you do that?) 7. 98 . Relate the ow rates A. Observe the partially open reciprocating pump and try to answer some of the questions above for this pump. 5. Find the ow rate through a water tap using a large measuring cylinder and a stop watch (what is the error involved in measuring ow rate?) 6. 4. Connect the piping network to the tap and measure the ow rate at A.B and C of the piping network to the total inlet ow rate 8. Build a piping network shown in the diagram using some of the available parts.3. In the hostel/ home try to predict the ow rate distribution through the network and see whether your experimental results match your predictions.B and C of the piping network.

046NRe (50000 < NRe < 106 ) (3000 < NRe < 3 × 106 ) 0. NRe decreases and at a particular value of NRe . tube or other conduit. • To determine the critical Reynolds number for transition from laminar to turbulent ow.125/NRe Procedure 1. Theory When a uid ows in a pipe. • To determine the friction-factor and to verify the relationship between f and NRe . when the velocity of a uid owing at a high velocity in a conduit is gradually decreased. For a pipe ow.2 0. the ow changes from laminar to turbulent.24 Nature of Flow Objectives • To visually observe laminar and turbulent ow patterns. Thsi type of ow is called turbulent ow. Allow the water to ll the equipment and adjust the ow rate to the lowest possible value. This may be rewritten as NRe = ρQD/Aµ = mD/Aµ where Q is the volumetric ow rate. m is the mass ow rate. D is the inner diameter of the pipe. Another signicant factor which is useful in the study of ow is the friction factor (f ) dened as the ratio of wall shear stress to the product of the density and velocity head. the uid moves without lateral mixing. thus disrupting the entire ow pattern. When the velocity of a uid owing in a conduit is gradually increased.0014 + 0. f= −0. For turbulent ow.32 f = 0. This type of ow is called laminar ow. Similarly. and µ is the uid viscosity. For laminar ow. as though a series of concentric conduits are sliding over one another. Adjust the ow rate of the dye solution so that its ow rate is the same as the velocity of water. At high uid velocities. V is the linear velocity. In such a ow. the ow may be laminar or turbulent depending upon the conditions of ow. 99 . the streamlines remain distinct from one another over the entire length. The type of ow and the magnitude of turbulence is given by Reynolds number which is a dimensionless parameter given by NRe = ρV D/µ. and A is the cross-sectional area. eddies form in the uids under motion causing lateral mixing and superimposition of turbulence on the primary motion of translation. the ow changes from turbulent to laminar. f = 16/NRe . f= ∆P gc D 2LρV 2 where ∆P is the pressure drop and L is the length of the pipe. the Reynolds number increases and at a particular value of NRe . At low uid velocities. this value of NRe is called upper critical Reynolds number. this value of NRe is called the lower critical Reynolds number. NRe = ρV D/µ where ρ is the uid density. 2.

3. Note the two tank heights for every ow rate and observe the ow for dierent ow rates indicated by the dye solution. 4. Measure the volumetric ow rate using a measuring vessel and a stop watch. 5. Increase the ow rate of water in small increments and repeat the above steps. 6. From the highest ow rate decrease the ow rate in small decrements, and repeat the above steps.

Results

1. For each run comment on the observed characteristics of the dye ow. 2. Calculate the volumetric ow rate, linear velocity, friction factor and Reynolds number. 3. Determine the critical Reynolds number for the transition from laminar to turbulent ow, when the ow rate is increased in small steps. Is it the same for the transition of turbulent to laminar ow when ow is decreased in small steps? 4. Plot the graph of f versus NRe and comment on the graph. McCabe, W.L., Smith, J.C. and Harriott, P., "Unit Operations of Chemical Engineering", 5th Edition, McGraw Hill International, 1993.

100

**25 Frictional Losses in Pipe Fittings and Valves
**

Objectives

1. To determine the frictional losses across pipe ttings in a piping network 2. To determine the frictional losses across valves in a piping network

Theory

The resistance oered by a tting is expressed as equivalent to the resistance oered by a length of a straight pipe of the same diameter as that of the tting. This length is called the equivalent length of the tting and length is expressed as the number of diameters of the pipe. Another method of expressing the resistance or frictional losses (FL) in ttings is by the number of velocity heads in a pipe of the same diameter

F Lf itting = Kv 2 2g

(25.1)

where K is the frictional loss constant, v the velocity and g the acceleration due to gravity. The pressure dierence across tting can be measured by a manometer or a pressure transducer

Procedure

1. Start the pump and wait until water ows in all sections of the piping network of interest in a steady state. 2. When steady is achieved measure the readings in the manometers across the ttings of interest. 3. Find ow rate of water. Find the frictional loss across each ttings and express the losses in terms of equivalent length and velocity heads.

101

**26 Viscosity Measurement Objectives
**

1. To measure the viscosity of a polymer solution using a Brookeld viscometer 2. To nd the viscosity at various concentrations of the polymer

Theory

The resistance oered to ow is related to the viscosity of the liquid. A Brookeld viscometer uses this principle to determine the viscosity of a liquid.

Procedure

1. Familiarize yourself with the various adjustments on the Brookeld viscometer (rpm, spindle, start/stop etc?) 2. Prepare a solution of the given polymer in water 3. Determine the dial reading for that solution. 4. Convert the dial reading into viscosity using the monogram for the viscometer.

102

1) where P is the power utilized for agitation ρ.27 Agitation and Mixing Objectives 1. measure the impeller speed. Vary the agitation speed using the variac. Represent the relationship between Power number and Reynolds number. Procedure 1. for an agitated system is given by : NRe = ρN d2 µ (27. Np . impeller diameter and the temperature.2) where µ is the uid viscosity. the impeller speed and d. Also. the uid density. 4. is given as: Np = P ρN 3 d5 (27. the impeller diameter. N . graphically. To relate the power number and Reynolds number in an agitated system Theory The Power number . To measure the power number for a agitated system 2. 103 . The torque developed can be measured by the dynamometer arrangement 3. 5. The Reynolds number NRe . Find the Power number and the Reynolds number for each run 6. 2. Place the given viscous liquid in a mixer system and agitate it by setting the impeller speed to a particular value.

28 Two Phase Flow in Vertical Tubes Objectives 1. surface tension and viscosity. 104 . 28. To investigate experimentally the relation between gas ow raye and the gas volume fraction (void fraction) for the slug ow regime in two phase gas/liquid ow in a vertical tube.1: Two-phase ow regimes in a vertical tube: (a) bubble. depending on many factors. Introduction Two phase gas / liquid ow is important in a variety of chemical engineering applications such as the simultaneous transport of the gas and oil in horizontal pipelines or a vertical wells several ow regimes can occur. and (d) mist ow. there are four principal ow regimes shown in Fig. In each case. Figure 28. To visually observe the motion of a single slug and investigate experimentally the relation between the slug velocity and slug dimension. the gas is shown in white and the liquid is shaded or black For vertical pipes (the situation here). (b) slug.1 and which occur successively at ever increasing gas ow rates. 2. including the orientation of the pipe the individual magnitudes of the liquid and gas ow rates and physical properties such as density. (c) annular.

namely about 1.3) 105 .2) Now. the liquid density plays only a small role in determining the shape of the slugs. where A is the cross-sectional area of the tube. In this regime. 28(a) is now shown enlarged in Fig. 28(b) which shows a slightly dierent situation: that of a single bubble. The liquid phase is still continuous.1 against both experiment and theory and possibly to determine a more appropriate value of the constant than 0. Davies and Taylor[2] used on approximate analytical solution that gave (28.2 + 0. there will be an upward liquid velocity ULm across a plane A-A just ahead of gas slug.35 The situation of Fig.1. Under circumstances. In general. the actual rise velocity of the slug will be Us = 1. 3.2ULm . Bubble ow in which the gas is dispersed as small bubbles through out the liquid which is the continuous phase. as shown by Nickin. and Davidson [1] provided that the Reynolds number between slugs exceeds 8. near the "nose" O of the slug-at the center of the tube. Further.2 G+L G+L + Ub = 1. Mist ow in which the velocity of the continuous gas phase is so high that it reaches as far as the tube wall and entrains the liquid in the form of droplets. The mean liquid velocity at A-A is therefore ULm = (G + L)/A. Wilkes. 28(a). in a tube of internal diameter D. you will also be attempting to test equation 28. especially in the tube of larger diameter: also. the situation is one of the potential ow in the liquid. surface tension and viscosity are possibly relatively unimportant. The slug is no longer rising in a stagnant liquid as in Fig. namely G=L. in which the gas (air) and liquid (water) are traveling upwards together at individual volumetric ow rates G and L respectively. Principles and Theory The general situation is shown in the Fig. where the velocity is the highest-the liquid velocity will be somewhat larger. but is important if pressure-drop calculations are needed. 28(b) but in a liquid whose mean velocity just ahead of it is ULm . the total upward volumetric ow rate of liquid across A-A must be the combined gas and liquid ow rates entering at the bottom.35 gD in which g is the gravitational acceleration. For liquid such as water and light oils that are not very viscous. consider Fig. Annular ow in which the fast moving gas stream is now a continuous phase that encompasses central portion of the tube with the liquid forming a relatively thin lm on the tube well. Therefore. As part of this project.1) Ub = 0. By applying continuity and considering the gas to be incompressible over short distances. which is moving steadily upwards with a rise of velocity Ub in an otherwise stagnant liquid. by conservation of the gas we must have G = Us A (28. In the experiment. 28(c). 4. 2. Next.000. you will be investigating the slug ow regime for the ow of air and water in the tube. Slug ow in which the individual small bubbles have started to coalesce together in the form of slugs.35 L L gD (28.

(c) bubble 106 .Figure 28. (b) bubble rising in stagnant liquid.2: Two-phase ow in a vertical tube: (a) gas and liquid ascending.

eliminating Us between Equations 28. By measuring time taken to move up a known distance. Equation 28. Equipment A 12. Use wide spectrum of slug lengths as possible and note down the slug length as accurately as you can in each case. Compare with theory and discuss. For single slugs of air in stagnant water. Two ow meters for measuring ow rates of air and water (0-20 Ls−1 and 0-2 Ls−1 ) are connected to respective supply line. Therefore. is much greater than that of gas. the Pressure drop is given to the rst approximation by P1 − P2 = ρL gH(1 − ) (28. A one HP motor pump is used in this experiment Values are for controlling the air and water supply.5 m is connected to air and water supply systems.4 gives the void fraction. Data Analysis 1. determine the rise velocity. with L = 0. For steady slug ow .5 would include the wall friction on the liquid "pistons" between successive gas slugs.35 gD A A (28.4) If G and L are known. the slug rise velocity. Compare with theory and discuss. Repeat for the variety of ow rates. which is very important in determining the pressure drop in a tube of height H .5) A secondary correction to Equation 28. ms−1 . form isolated single slugs. and (by quickly closing the valves in the tube) the void fraction.5 mm diameter plastic tube of length 1. . m3 s−1 . Take plenty of measurements (at least 30).2 and 28. 2. Us .2 + 0.3 we obtain G+L G = 1. Also note that the weight of the liquid .plot gas volume fraction with the gas ow rate. Ub against the slug length to see if they are correlated. which occupies fraction (1 − ) of the total volume. Plot the rise velocity. By turning the air ow on and of suddenly. Measure the volumetric owrate of air G. Operate with a steady continuous steady continuous stream of air so there is no net water ow rate: that is.in which is the void fraction (the fraction of the total volume that is occupied by the gas). Hence. 2. 107 . Procedure 1.

If the instrument is sensitive enough. In order to reduce heat ow to or from the surroundings. Figure 29. adsorption or in a chemical reaction. stirring of the contents would also be controlled and its eect should be monitored in a blank experiment. Calorimetry can be of two types: adiabatic or isothermal. it is used for the determination of heat capacities. dissolution. H = Resistance Heater.1. dilution. S = Polypropylene Stopper. minute "heat leaks" are not uncommon. D = Glass Dewar Flask of capacity 100 ml. However. In an adiabatic calorimeter no heat is exchanged with surroundings and hence temperature change is to be monitored during the process occurring in the calorimeter. Figure 29. T = Temperature Sensor 108 . A vacuum ask/Dewar ask is used as an adiabatic calorimeter.1: A schematic diagram of a Calorimeter. crystallization. In addition. Care should be taken so that "heat leak" does not occur through either the lid of the Dewar ask or openings in the lid.29 Determination of Partial Molar Enthalpies by Adiabatic Calorimetry Objective To determine the heat of mixing of binary system by adiabatic calorimetry and the partial molar enthalpies of two components. the Dewar ask itself should be placed in a constant temperature container such as a large thermostat or insulated box whose temperature should be regulated as close to the contents of the Dewar ask as possible. In such a case the accuracy of measurement of any physical property using a calorimeter depends on the accuracy of temperature measurement and how good the adiabatic shield is. ST= Stirrer. Introduction Calorimetry involves measurements of enthalpy changes in various processes like mixing.

Add a known volume (take weight) of the second liquid (2). Note this ∆Tm against the mole fraction x1 of liquid 1 in the nal mixture. 109 . the other quantities being known experimentally. 3. Stir and note the nal and steady mixture temperature T2 .2) where V is the voltage drop across the heater resistance. then: Q = mCp ∆T + K∆T (29. and generating experimental measurements) so that you obtained a range of ∆Tm and Cpm corresponding to mole fraction x1 ranging from 0 to 1.1 the calorimeter is provided with a heating coil (in the form of a resistor). stopper and walls of the ask absorb some heat it is necessary to know the calorimeter water-equivalent. The total volume of the mixture should be about 85-90 ml. K .If ∆T is the observed temperature change. Next the heating coil is switched on and the specic heat (Cpm ) of the mixture is measured as outlined above in section "B". Heat of mixing determination. temperature sensor. "Joule heating" will cause the temperature of the system to increase by (say) ∆Th (◦ C). The amount of energy supplied (Q) is Q = IV t in Joules (29. the heating coil is kept "o". 5. 4.1. If a known current I (amp) is passed for time t (sec) through the heating coil. During this part of the experiment. heater. Find calorimeter constant K by the procedure outlined above. Combining Equations 29. Repeat the two previous steps (nding the heat capacity of a pure liquid. this will be negative or positive depending on the sign of heat of mixing of the system. Experimental Measurements 1. Q (Joules) is supplied to the calorimeter containing (say) m gm of water of heat capacity (Cp (J/g K)). Allow thermal equilibrium to be attained and note the initial temperature T1 .Procedure To nd water-equivalent of calorimeter Since the various parts such as stirrer. Again ∆Th should be at least 3-4◦ C. 6.1) Hence K can be calculated from Equation 29. For this purpose a known amount of heat. Cp of a pure liquid of a solution may be determined (the other quantities being known experimentally).3) Using this equation. To nd heat capacity of a pure liquid or a solution As shown in Figure 29.1 IV t = mCp ∆T + K∆T (29. Add a certain volume of (but take weight) rst liquid (1) to the calorimeter. The resultant temperature change due to mixing is ∆Tm = (T2 −T1 ). 2.2 and 29.

Calculate the partial molar enthalpies at the composition x1 = 0. if isothermal conditions of mixing were to be maintained. an amount of energy Qm would have to be added (or withdrawn). n2 = moles of components 1 and 2 in the mixture). (n1 . ∞ ∞ 3. x1 curve with reference to the molecular properties of the components forming the mixture. Heat of mixing ∆hm per mole solution. Plot ∆hm vs.5 and H1 & H2 . at mole fraction x1 is given as ∆hm = Qm /(n1 + n2 ) Joules/mole. where Qm = (mCpm + K)(−∆Tm ) (29.Note that mixing occurs under non-isothermal conditions. 4. It follows.4) where m = total mass of the mixture. Estimate the quantity Qm for each composition of the mixture. therefore. Calculations 1. 2. x1 . Take at least 4-5 compositions. Comment on the nature of the ∆hm vs. 110 .

The equilibrium state is indicated by the constancy of both the thermowell temperature and of the vapour condensation drop-rate through the drop-counter.2) (where T in in K. Accurate data on equilibrium vapor pressures can be determined over a range 100 to 760 mm Hg using a specially designed glass ebulliometer connected to a manifold and pressure control system. The above equation is called Clausius-Clapeyron equation where. The pressure of the ebulliometer is regulated via a stop-cock. an assumption must be made regarding the dependence of the group (∆Hv /∆Zv ) on temperature. The simplest approach is to assume that the ∆Hv /∆Zv is constant and then Equation 30. T = ◦ C. charged to ll the bulb of the ebullometer. A simple modication of the equation which has been widely used is known as Antoine equation: B ln P = A − (30.1.3) T +C As an approximation at low pressures (< 1 atm). The liquid stream along with the condensed vapor is recirculated till equilibrium is attained. Electrical heating is regulated in order to minimize superheating and the ebulliometer is adequately insulated in order to minimize heat loss resulting in any subcooling of the liquid.0. Experimental Procedure 1. When the bulb is electrically heated. pressure in both phases leads to the Clausius-Clapeyron equation: d ln P ∆H =− d(1/T ) R∆Zv (30. or solution whose vapour pressure is to be measured is.1) Most vapour pressure estimations and correlation equations stem from integration of Equation 30. Introduction When the vapor phase of a pure uid is in equilibrium with its liquid phase. temperature. When this is done. B is given as ∆Hv /R∆Zv (∆Hv = enthalpy of vaporization). if ∆Zv is taken as 1.1 on integration becomes (A being the integration constant: ln P = A − B T (30. and ∆Zv = Zvap − Zliq . 111 . the pressure being recorded by means of an absolute manometer. 2. the equality of chemical potential. 1/T . C = Constant. the latent heat of vaporization can be directly obtained from the slope of the plot of ln P vs. slugs of vapor bubbles with entrapped liquid rise in the tube (Cottrell Pump) to the ask chamber and are poured on the inner surface of the thermowell where vapour bubbles get disengaged from the liquid. The sample of the liquid.30 Ebulliometric Determination of Vapour Pressures Objectives 1. To determine the vapour pressure at various temperatures for a pure substance and to calculate the correlation constants in the vapour pressure equation. Estimation of the latent heat of vaporization for the substance from the vapour pressure data. Z being the compressibility factor).

3. Allow at least 20-25 minutes for this. 5. Determine the correlation constants in the vapour pressure equation. but note the change of temperature with time (not needed to be reported in journal) so that you know when a steady temperature is reached. Adjust the heat input to the ebulliometer bulb using the rheostat so that you obtain a drop rate in the intermediate range ( 40-90/min). If the units of P are changed from mm Hg to atm or Kgf/cm2 . Experimentally both these extremes need to be avoided as these may make the system exist either in the supercooled or superheated region. no more than a change by a graduation is recommended at a time. 4.2. Once temperature steadies. Estimate latent heat of vaporization from the plot in (1). count the drop rate (per minute) of condensed vapour. Plot ln P vs. 1/T . How does the latent heat change with increasing temperature and pressure over a wide range? Under what condition is ∆Hv zero? Why ? 6. and note the stable temperature. 3. This drop rate is proportional to the steady state amount of the substance in the vapor phase (which is. 112 . keeping the same pressure. The temperature measured under such a condition will provide a relatively accurate equilibrium value of temperature. Obtain P vs. Report the average of the two temperatures as the equilibrium temperature corresponding to the pressure of the manifold. Experimentally low drop rate (< 30/min) correspond to low values of x. 2. The latent heat of vaporization is generally seen to be dependent on properties such as molecular weight and polarity. At an intermediate drop rate the system is likely to be in the two-phase region with a medium quality. being condensed back into liquid). wait for system temperature to stabilize and then measure the drop rate. and obtain another drop rate preferably within the same range. while very high droop rates (> 110/min) indicate high value of x. 7. the system will on its own adjust to the corresponding equilibrium temperature. and hence also the drop rate of condensed vapor). After any such change. which will yield an inaccurate equilibrium temperature measurement for a given pressure. T data for at least 8 pressures in the range 100-760 mm Hg. Once you obtain a stable drop-rate in the intermediate range (and a corresponding temperature). how does the behavior of the curve change? 4. Once the pressure in the manifold is xed at any value. The rheostat is very sensitive. For vapour-liquid equilibrium the system T remains constant as quality (x) going from 0 to 1. change the rheostat reading by half a graduation (either increase or decrease as needed. Calculations 1. 6. of course. Explain why these properties are determinant to the enthalpy of vaporization. note that increase in rheostat reading would increase heat input. 5.

5 in 31. Experimental determination of IDACs is based upon the following theoretical consideration. If the vapour phase is assumed to be ideal and the Poynting correction is negligible then the total system pressure at vapour-liquid equilibrium is given by: ◦ ◦ P = γ1 P1 x1 + γ2 P2 x2 (31. This equation is dierentiated dx2 dγ1 dγ2 dP ◦ ◦ = P1 x1 + γ1 + P2 x2 + γ2 dx1 dx1 dx2 dx1 (31. Theory The greatest deviation from ideal solution behaviour occurs at innite dilution.1) at constant temperature to give: Pi◦ = sat vapour pressure of the ith species at the given temperature.3 the value of γ1 can be obtained from isobaric data using the relation. appropriate indices to the degree of non-ideality of a solution. To estimate the parameters in the activity coecients correlations such as Van Laar/Wilson.5) ∞ Substituting 31.31 Ebulliometric Determination of the `Innite Dilution Activity Coecient' (IDAC) Aim 1. To determine the value of the "Innite Dilution Activity Coecients" (IDAC) of a binary at 1 atm pressure using dierential ebullometry and the limiting slope method.4) P Evaluated at x1 = 0.3) The following general relationship of the partial derivatives exists for the variables T . therefore.2) If we let x1 approach zero and use the following relations: dx2 = −1. Further. ∞ γ1 = 0 0 P2 − (dP2 /dT )(dT /dx1 )∞ P 0 P1 (31. this becomes ∂P ∂x1 ∞ =− T ◦ ∂P2 ∂T ∂T ∂x1 ∞ P (31. P and x1 : ∂P =− ∂x1 ∂P ∂T x1 ∂T ∂x1 (31.6) 113 . 2. dx1 dγ1 is nite at x1 = 0 dx1 ∞ γi = γ2 → 1 x2 → 1 dγ2 /dx2 → 0 0 P → P2 Hence we get: 0 P2 + (dP/dx1 )∞ 0 P1 (31. The innite dilution activity coecients are. the knowledge of innite dilution activity coecients allows phase equilibrium calculation to be performed as they may be used to determine the parameters of the activity coecient model suitable for the binary mixture.

Further dT /dx1 |∞ can be obtained from the limiting slope of the T vs x1 curve as x1 → 0 by P plotting the solution boiling temperature (T ) versus mole fraction (x1 ) Procedure Accurate data on innite dilution activity coecients can be obtained using ebulliometers. Repeat the above for the other dilute and (with species 2 in dilute solution in species 1) to ∞ calculate γ1 (This data may be taken from the complementary experiment carried out by other groups). At what temperature have γ1 and γ2 have been calculated? Does your system exhibit positive or negative deviation from Raoult's law? 5. After the temperature has steadied for each ebulliometer. Calculations 1. P 1. Drop rate for each dilute solution separately. 3. Calculate γ1 using this slope and correlations developed in the preceding section. each charge having a dierent concentration of the species (solute 1) present in dilute amounts. x1 ) to nd the slope of the ∞ best straight line. 0 0 P2 B dP2 = dT (T + C)2 (31. the temperature should alter by a very small amount (if at all) and at its altered steady value measure the average drop rate as before. Plot bubble point temperature vs. 2. 3.e. 114 . Set the pressure of the entire manifold at the xed value (typically it may be atmospheric) and switch on the heating supply to each ebulliometer.7) where B and C are the Antoine constants for the component 2. For each ebulliometer obtain at least 3 − 4 sets of temperature and drop rate (which should not exceed 100/min) measurement. count the average drop rate of condensation of vapor per minute and record it against the temperature.If the Antoine's equation for vapour pressures is used then. very dilute solutions may be used. Three or four ebulliometers are connected to a manifold and a common pressure control system. The pure solvent (2) is charged to one of the ebulliometes and very dilute solutions of known concentrations of solute (1) (typically. Ideally. if available. Determine the Van Laar or Wilson's parameters and compare with literature data. ∞ ∞ 4. concentration (i. thus increasing the accuracy of determination of the slope dT /dx1 |∞ . in the range 0 − 5 mol percent) are charged to the remaining ebulliometes. Plot temperature vs. Alter the heat input to each ebulliometer by a very small amount (typically by about half a graduation on the rheostate controlling the heat input) and record any ensuing change of temperature. T vs. Extrapolate to zero drop rate to get the bubble point temperature of solution (why?) 2. Since extremely small boiling temperature dierences can be detected between that of the pure solvent and that of solutions.

1: Orientation of surfactant molecules Interfaces are produced extremely quickly in processes such as foaming.e. but also the kinetics of the interface formation. The equilibrium value of the surface tension decreases as the number of surfactant molecules 115 . As a result of this construction the surfactant molecules accumulate at the surface. Figure 32. the static surface tension is obtained. In such processes it is not just the equilibrium value of the interfacial tension that is the decisive inuence. Dynamic surface tension With conventional surface tension measuring methods. Apparatus and Instruments Volumetric asks. distilled water. conical asks. Theory 1. Chemicals Sodium dodecyl sulphate solution. This is because of the molecular construction of the surfactants: they consist of a hydrophilic (water-attracting) "head" and a hydrophobic (waterrepelling) "tail". As can be seen. the "tail" projects from the surface and causes a reduction in the surface tension. i. Figure 32.2: Time dependence of dynamic surface tension 2. pipette. at the start the surface tension falls rapidly and only approaches an equilibrium value after some time has passed. the concentration also has a decisive inuence on the surface tension. etc. The molecular mobility of the surfactants used assumes a considerable inuencing factor on the formation of the surface tension. such as the Wilhelmy plate method. bubble pressure tensiometer. The following illustration is a schematic representation of the surface tensions of two surfactant solutions as a function of the surface age. Surfactant solutions require a much longer time than water and other liquids to achieve this dynamic equilibrium. beakers. a statement is made about a completely formed surface which is in dynamic equilibrium.32 Determination of the Dynamic Surface Tension of a surfactant by using Bubble Pressure Tensiometer Aim To determine the dynamic surface tension of given surfactant solution using maximum bubble pressure tensiometer. acetone. Dependency of the surface tension on the concentration In addition to the chemical structure. printing or coating. cleaning.

The bubble nally escapes from the capillary and rises. At this point the air bubble radius is the same as that of the capillary. the hydro-static pressure in the capillary p0 . 2. the so-called "micelles".g. Initially the pressure is below the maximum pressure. The bubble is formed.5: Bubble formation with time 1. The concentration at which this eect occurs is known as the "critical micelle formation concentration" (CMC). If the concentration is further increased from this point then the surfactant molecules will accumulate within the solution and form aggregates. the radius of the air bubble becomes larger. 116 . It achieves its nal value when the surface is completely occupied and oers no place for further molecules. The cycle begins again with the formation of the next bubble. The bubble pressure method An easy-to-use method for determining the dynamic surface tension is the method of measuring the maximum bubble pressure.accumulating at the surface increases. This means that methods for measuring the dynamic surface tensions should only be used above the CMC.4: Ranges of static and dynamic measuring methods 3. the inner radius r of the capillary and the surface tension: σ= (ρmax − ρ0 )r 2 3. The following relationship exists between the maximum pressure ρmax . the radius of curvature of the air bubble is larger than the radius of the capillary.3: Schematic image of a micelle Figure 32. The pressure decreases again. The following illustration shows the measuring ranges of static and dynamic methods (e. In such a case the concentration only inuences the chronological function of the surface tension and no longer has any inuence on its static value. It is an important characteristic for surfactants. the air bubble forms an exact hemisphere. The following illustration shows the pressure curve during bubble formation plotted as a function of time: Figure 32. The pressure curve passes through a maximum. After the maximum the "dead time" of the measurement starts. The gas bubbles enter the liquid through a capillary whose radius is known. During this process the pressure passes through a maximum whose value is recorded by the instrument. 4. In a bubble pressure tensiometer gas bubbles are produced in the sample liquid at an exactly dened bubble generation rate. the bubble pressure method): Figure 32.

Measure the dynamic surface tension of pure acetone and pure water. Figure 32.4. Record the observations in a tabular form and plot a graph of dynamic surface tension of SDS solution v/s bubble frequency. What are the dierent methods used for measurement of surface tension? Explain in brief. 2. At higher frequency the surfactant molecule does not have adequate time to diuse to and orient them at the gas/liquid interface. Hence the surface tension increases. Make a 50 mM Sodium dodecyl sulphate (SDS) solution and measure its surface tension at a bubble frequency of 1 Hz. In case of multi component solution. Repeat the third step by increasing the bubble frequency by one unit. 5. 117 . Variation of surface tension with the bubble frequency For pure solvents the dynamic surface tension does not change with the bubble rate. till the bubble frequency is 10 Hz. 3. Increase the bubble frequency to 2 Hz and note the surface tension. What are the dierent types of surfactants? Explain each type with examples. 2.6: Surface tension versus bubble frequency Experimental Procedure 1. the surface tension increase with the increasing bubbling frequency. Questions 1. 4.

The Van Laar equations are log γA = 1+ a aXA bXB 2.3) 4. log γB = 1+ b bXB aXA 2 (33. The Gibb's-Duhem equation for the binary system for checking thermodynamic consistency of the data by the integral test: 1 ln 0 γ1 dXA = 0 γ2 (33.33 Vapour Liquid Equilibrium Aim To determine the vapour-liquid equilibrium data for the given binary system. Equilibrium data represent the composition of the mixture in the vapour phase (Y ) and that in the corresponding equilibrium liquid phase (X) at equilibrium. The vapour-liquid equilibrium data are presented as equilibrium compositions: YA = PA γA XA = KA XA πA YA /(1 − YA ) XA /(1 − XA ) (33. The vapour from this rises to the equilibrium chamber. Theory Vapour-liquid equilibrium data are the basic information of the system required for the design of equilibrium stages of a vapour-liquid separation equipment like distillation. The compositions are presented in mole fractions of the more volatile component (A). Therefore the data are reported under isothermal or isobaric conditions. B = less volatile component). 1. The binary liquid mixture is vapourized by an electrical heating coil in the vaporizer at a slow rate.4) Many systems form an azeotrope where the equilibrium vapour and liquid compositions are the same i. isobaric data are required more often because industrial separations are carried out at constant pressure. However.2) 3. 1. (A = more volatile component. Relative Volatility: αAB = (33. (2) Flash chamber or Equilibrium chamber.1 is known as a vapour-liquid equilibrium still and has two essential parts: (1) Vaporizer. To check the thermodynamic consistency of the data. To present the thermodynamic characteristics and constants of Margules equation for the given system.e. YA = XA Experimental setup The apparatus shown in Figure 33. Equilibrium compositions are functions of temperature and pressure. Vapour and liquid equilibrium at the temperature and pressure 118 .1) 2. 2.

1: Schematic diagram of VLE setup 119 .Figure 33.

The vapour and liquid phases separate from each other in the ash chamber. Allow the system to approach equilibrium.I. More Volatile Component (A): 2. 2. The temperature or the chamber is recorded by the thermometer which extends well inside the equilibrium chamber. through which the mixture again goes back to the vaporizer. Report XA and R. Drain out about 40 ml of mixture from the still and add about 40 ml of less volatile component. Take at least six samples.I for the whole range as follows: 120 . Prepare the mixture of various compositions and determine the R.of the chamber is established. Prepare a calibration chart of composition vs. Procedure 1. This mixture should be lled in the still through either of the limbs. Repeat steps (1) to (5) and record the composition and temperature readings. Switch on the power and slowly increase the power input in slow steps. Take the liquid and vapour samples and determine the refractive index (or density). covering whole range of compositions.I. Observations & Results 1. The pressure of the chamber may be regulated by connecting the vapour line to vacuum or pressure header.) or density. Less Volatile Component (B): 3. determine XA and YA . The still may be drained through the feeder line and may be charged through either the vapour or the liquid line. 5. 6. Heating should be regulated so that there is no entrainment or foaming of the mixture from vaporizer to the ash chamber. refractive index (R. Check carefully that the electrical coil is completely submerged in the liquid (to avoid ignition) and the mixture is more than 2/3rd level in the vaporizer. 3. The liquid ows down the liquid line through a water cooled joint to the feeder line. or density. Prepare about 200 ml of mixture of A and B. The circulation of the vapour and liquid will soon get established. for the two pure components A and B and their mixtures with XA varying from 0 to 1. This will be indicated by constant temperature of the thermometer at least for ve minutes.I. Also record the temperature and from R. (or density). The experiment should be started with the mixture richer in more volatile component (say 160 ml of A and 40 ml of B) so that in subsequent readings temperature increases.I at 30◦ C A B 4. Properties of components (from literature/experimental) Component Density at 30◦ C Molecular Weight Boiling Point R. 4.

γB . XA (should be less than 20% due to experimental error). ◦ C XA Y 6. γA . ln γB (on the same graph) and ln(γA /γB ) vs XA (as another graph) and check for thermodynamic consistency. KA . X .I. Report t − X − Y as follows: t. Report in a data table the following: t. Plot ln γA .XA R. Calculate KA . Y . 5. Find the dierence in the positive and negative areas of ln(γA /γB ) vs. ln(γA /γB ). γA and γB . Calculate the Van Laar constants a and b from a = log γA 1 + b = log γB 1 + XB log γB XA log γA XA log γA XB log γB 2 2 Comments 121 . 8. 7.

Analytical reagents: (a) 50 ml of 2% sodium carbonate mixed with 50 ml of 0. The incubation time is very critical for a reproducible assay. The nal volume in each of the test tubes is 5 ml.37% sodium potassium tartarate solution. Most proteins estimation techniques use Bovin Serum Albumin (BSA) universally as a standard protein. 2.Ciocalteau reagent which consists of sodium tungstate molybdate and phosphate.56% copper sulphate solution mixed with 10 ml of 2. Reagents Required 1.Ciocalteau reagent solution (1N) Dilute commercial reagent (2N) with an equal volume of water on the day of use (2 ml of commercial reagent + 2 ml distilled water) Principle The phenolic group of tyrosine and trytophan residues ( amino acid) in a protein will produce a blue purple color complex . because of its low cost.2 ml of reagent Folin Ciocalteau solution (reagent solutions) to each tube and incubate for 30 min.34 Total Protein Estimation by Lowry's Method Objective To determine the concentration of proteins by Lowry's method. The BSA range is 0. with maximum absorption in the region of 660 nm wavelength. BSA stock solution (1mg/ml). This solution is incubated at room temperature for 10 mins. Zero the colorimeter with blank and take the optical density (measure the absorbance) at 660 nm.1 N NaOH solution (0. Procedure 1.5 is essential. Thus the intensity of color depends on the amount of these aromatic amino acids present and will thus vary for dierent proteins. 5. Dierent dilutions of BSA solutions are prepared by mixing stock BSA solution (1 mg/ ml) and water in the test tube as given in the table. carbohydrate.) (b) 10 ml of 1. Prepare analytical reagents by mixing 2 ml of (b) with 100 ml of (a) 3. From these dierent dilutions. Mix the solutions well. high purity and ready availability. 122 . 4. The method is sensitive down to about 10 µg/ml and is probably the most widely used protein assay despite its being only a relative method . pipette out 0. 3.05 to 1 mg/ ml. with Folin. EDTA. Then add 0. Plot the absorbance against protein concentration to get a standard calibration curve. 2. Folin . nonionic and cationic detergents. subject to interference from Tris buer. The reaction is also dependent on pH and a working range of pH 9 to 10.4 gm in 100 ml distilled water. lipids and some salts.2 ml protein solution to dierent test tubes and add 2 ml of alkaline copper sulphate reagent (analytical reagent).

2 0.75 4.L.8 1.2 0. Lowry.4 0.5 1 2 3 4 5 4. Compare Folin-Lowry method with other methods of protein estimation. Check the absorbance of unknown sample and determine the concentration of the unknown sample using the standard curve plotted above. K.6 0.. 48:422 (This modication makes the assay linear over a larger range than the original assay) 3. J.2 0. O. Farr. (1972). R.J. A. Cambridge University Press.Chem 193: 265 (The original method).2 0. (2000) "Practical Biochemistry: Principles and Techniques". Anal.. N. 2.2 0.2 0. Biochem. Beer-Lamberts law 2.2 0.1 0. CuSO4 Lowry reagent O.E.2 0. and Walker. 123 .25 0.05 0. Wilson.2 0.0 0. and Randall.Biol. Sample vol Alk.2 0.2 2 2 2 2 2 2 2 0.J.. Hartree E.2 Write short notes on the following points in the report: 1.D. (ml) (ml) (mg/ml) (ml) (ml) (ml) 600 nm 0.6.2 0.H. (1951) J.5 4 3 2 1 0 0.2 0.2 0. Rosebrough. BSA Water Sample conc. References 1.

such as carbonate and bicarbonate. volumetric asks. or acetate and acetic acid.11 ranges. 20 mM glycine 2. measuring cylinders. 20 mM glycine 2. From the Henderson-Hasselbalch equation an expression for buer capacity (β = d[A− ]/d[pH]) may be deduced. Since the pH range of interest to the biochemical engineer is 3 . Glycine-NaOH buer system: 1. distilled water. 124 . addition of small amounts of strong acid and strong base result in removal of only small amounts of the weakly acidic or basic species. The quality of a buer is dependent on its buering capacity (resistance to change in pH by addition of strong acid or base) and ability to maintain a stable pH upon dilution or addition of neutral salts. wash bottle. pH meter. this can be ignored. Below pH 3 and above pH 11 the concentration of the ionic species of water must be included in the equation. a Requirements Buer stock solution (concentrated). and this basic form of equation is accurate between the pH ranges of 3 to 11. there fore there is little change in the pH: HA(acid) ↔ H + + A− (conjugate base) B (base) + H + ↔ BH + (conjugate acid) The pH of a solution of a weak acid or base may be calculated from the Henderson-Hasselbalch equation: pH = pKa + log a [basic species] [acidic species] (35. beakers. Because of the following equilibria.1) The pK of a buer is that pH where the concentrations of basic and acidic species are equal. 200 mM HCl Theory The observation that partially neutralized solutions of weak acids or weak bases are resistant to pH changes on addition of small amounts of strong acid or strong base leads to the concept of "buering". and pipettes. 200 mM NaOH Glycine-HCl buer system 1. Buers consist of an acid and its conjugate base.35 Determination of pKa by pH Titration Method Objective To determine the pK values and buering capacity of buer solutions.

Procedure

1. pH Measurement: Mix all solutions thoroughly. The pH measurement may be made in original beakers. Do not change any control on the pH meter except as directed. With the meter on stand by, rinse the electrode with deionized water, gently shake o the excess water, and immerse the electrode in the sample solution. Switch the meter to the pH mode, allow the reading to stabilize, and record the pH. Switch the meter back to the standby mode, rinse the electrode again, and leave the electrode immersed in deionized water. Repeat this procedure for all samples. 2. Glycine-NaOH buer system: Prepare 50 ml 20 mM glycine solution and 100 ml of 200mM NaOH solution. Calibrate the pH meter with standard buer solution at room temperature. Take 50 ml of glycine solution in a beaker and add 0.5 ml of NaOH solution and shake well to mix. Note the change in pH. Add subsequent quantities of NaOH with an increment of 0.5 ml each time and note observed pH at regular intervals. Take about 30-35 readings and generate the following observation table: Volume of NaOH added (ml) Observed pH 0.0 1.0 1.5 2.0 2.5 .

**Results and Discussion
**

1. Plot the titration curve for the given buer system. 2. Estimate the pK for the dierent ionic species.

a

3. Derive Equation 35.1. Derive an equation for the buering capacity in terms of Ka and [H + ]. 4. When is β maximum and what is its value at that condition? 5. List a few biological buers and their range of operation. How do biological systems (cells tissues etc.) maintain pH?

Further Reading

1. Read up the theory on buering of blood. 2. How does the pH meter work? 3. Buers: Principles and Practice, in Methods in Enzymology Vol. 182, Academic press, 1990. 4. L. Styrer, Biochemistry, W.H. Freeman, 1995. 5. D.Freifelder, Physical Biochemistry, W.H.Freeman, 1976 125

**36 Aseptic Culture Techniques
**

Objectives

To demonstrate the presence of microorganisms everywhere in the environment.

Introduction

In microbiological and biochemical engineering studies, one almost always deals with a pure culture or a mixture of known cultures, except perhaps in waste water treatment studies. Unless aseptic culture techniques are followed strictly, an originally pure culture will denitely become contaminated with other unwanted species. The use of a contaminated culture with unknown microorganisms will only lead to incredible results that are of little value. Thus, isolation and maintenance of a pure culture is of utmost importance in many microbiological studies. It is especially important to work with a well-characterized strain if the microorganism is used for a food preparation, as well as in antibiotic production where the product is to be taken internally. The need for a clean working environment in biological engineering studies is a must and cleanliness is the prerequisite for any meaningful work. The environment we live in is full of microorganisms capable of surviving in any condition. This experiment is aimed at introducing you to the presence of microorganisms in the environment with the use of a simple microbiological technique.

Requirements

Nutrient agar plates, and incubator (at 37◦ C)

Procedure

Obtain the prepared petri dishes containing nutrient agar medium from the instructor and expose them to the following: 1. Exposure the plate to air for 30 minutes 2. Touch with unwashed ngers. 3. Touch with ngers washed with water and soap 4. Touch with ngers dipped in ethanol. 5. Kiss with moist lips 6. Press against the lab door knob. 7. Press against the bathroom doorknob. 8. Smear a little yogurt or milk. 9. Press coins. 10. Press against a tap handle. 11. Cough vigorously from 4-6 inches away. 126

12. The plates should be labeled appropriately and incubated upside down at 37◦ C 13. Come back to the lab after 12 to 24 hours and note down what you nd on the plates.

Observations

There are actually many more numbers and varieties of microorganisms in our immediate environment than those appearing on the incubated plates. Some of these will not grow in aerobic conditions or on glucose, but will ourish in dierent media. When working with microorganism, it is important that the working environment stays as clean as possible. For example, a minuscule pu of mold spores can drift in air for an extended period of time and contaminate many subsequent experiments. Some of the spores can withstand even the temperature existing inside an autoclave and emerge from the sterilization process in dormant but viable forms. In general, the chance of contamination is proportional to the number of microorganisms in the environment when the aseptic procedures are undertaken. It is important in a shared laboratory setting to practice good aseptic techniques and keep the working environment clean. Although microorganisms can't be totally eliminated in our lab, their numbers can certainly be reduced drastically.

Questions

1. Describe the morphology of the colonies growing on the plates (color, texture, size, shape, elevation, number of colonies, etc.). 2. What is the role of agar in microbiological media? 3. Write a note on dierent types of microorganisms and their characteristics. 4. What are the methods available for the identication of microorganisms?

References

1. Ananthanarayan, R. Panikar, C.K.Jayaram, Textbook of Microbiology 5th Edn, Orient Longman, 2000. 2. Collins, Microbiological methods. - 5th Edn Butterworths, 1984

127

temperature.1 gm of p-nitrophynyl phosphate in 25 ml of carbonate -bicarbonate buer (prepared as above).01-mg/ml solution. Here we make use of following reaction which results in the formation of yellow coloured product.37 Kinetics of Alkaline Phosphatase Objective To study the kinetics of alkaline phosphatase.sodium bicarbonate buer: Dissolve 20 ml of 0.12 gm in 250 ml distilled water) to make up the volume 250 ml with pH 9 -9. The rate of an enzyme-catalysed reaction can be measured by: 1. Enzyme solution: Dissolve 10 mg of alkaline phosphatase enzyme in 10 ml carbonate bicarbonate buer to get 1 mg/ml stock solution. which requires a pH of 9-9. The rate of enzyme-catalyzed reaction is inuenced by dierent environmental conditions like concentration of substrate. including articial 128 . 4. which might involve measuring the formation of the product. The disappearance of substrate.1 ml of stock A and make-up the volume to 10 ml with buer to obtain 0. The assay is a measurement of a chemical reaction. or 2. There are two types of phosphatases depending on the pH environment in which they are active.2 2. Pipette out 0. an assay is necessary. The appearance of the product. 5 N sodium hydroxide solution (10 gm in 50 ml distilled water) 3. which is used for further dilution. Presence of inhibitors and concentration of the enzyme itself.12 gm in 100 ml distilled water) and 230 ml of 0.2 M sodium bicarbonate (4. In order to measure the activity of enzyme the rate of formation of product can be followed.2 for its activity. We are going to study the alkaline phosphatase. This enzyme catalyses the cleavage of phosphate group from a variety of compounds. Enzymes catalyse the reaction rapidly under mild conditions in contrast to inorganic catalysts. To study an enzyme. then amount of substrate disappeared or product formed is measured and this information will give the rate of activity of the enzyme per unit time. Procedure 1.2 M solution of sodium carbonate (2. Substrate stock solution: Dissolve 0.p-nitrophenol the concentration of which can be measured using a simple colorimeter using appropriate lter (420 nm) p-nitro phenyl phosphate → p-nitro phenol + phosphate Alkaline Phosphatase is an important enzyme in recycling phosphate within living cells. Theory Chemical reactions in biological systems occur in the presence of highly specic protein catalysts called enzymes. In a typical experiment the enzyme and substrate are mixed and allowed to react for specic period of time. Sodium carbonate . pH. The enzymes phosphatases catalyze hydrolysis of phosphate esters to free inorganic phosphate in biological systems.

5 Results 1. (mg/ml) Sub vol(ml) Enz. 4.6 2.5 0.9 1.0 2.5 0. Prepare the 0.5 0.5 ml of 5N NaOH in each reaction solutions to stop the reaction.5 4.0 0. 8.4 4. Mix substrate and enzyme solutions in given proportion and keep for 15 minutes.0 Stock 4. Prepare a serious of standard concentrations of p-nitro phenol in distilled water and measure theabsorbance values at 420 nm against blank. Linear graph methods like the Lineweaver-Burk plot can be used for easy determination of reaction parameters. 2. Using the mathematical relationship between initial rate and substrate concentration (Michaelis-Mentin equation).1 0. Run a series of reactions with constant enzyme concentration at various substrate concentrations and measure the rate of reaction. Read the absorbance at 420 nm.1 0. 7. Estimate Km and Vmax using Lineweaver-Burk plot.vol(ml) NaOH(ml) Absorbance 0. Make the substrate dilutions as in the given table. 2. Estimate Vmax from asymptote.8 1.5 1. Data used for a Lineweaver-Burk double reciprocal plot to calculate kinetic parameters.0 3.9 1.5 0. Plot reaction rate (v ) against substrate concentration. 3. calculate the rate of the reaction and calculate amount of p-nitro phenol formed per second.1 0.9 1.4 0.1 0. is yellow in basic solutions.9 0. Procedure 1.5 2. From the standard curve of p-nitro phenol.9 1. 9.1 mg/ml enzyme solution (stock b) from the stock solution.9 1.0 2.5 0. 6. reaction parameters like maximal reaction rate (Vmax ) and the Michaelis constant (Km ) can be determined from a hyperbolic graph.0 2. Std (ml) Buer (ml) Sub conc. One of the formed products p-nitro phenol.1 0. 4.5 3. Add 0. The appearance and intensity of yellow colour in the reaction solution thus indicates the degree to which enzyme has acted upon substrate.colourless substrate used in the present analysis p-nitro phenyl phosphate.1 0.0 1.0 2. 129 . Plot graph of rate vs substrate concentration 3. 5.

Wilson. Principles and Techniques. New York 2. 7.5. Lubert stryer. References 1. Describe the signicance of of parameters: Michaelis-Menten constant (Km ) and Vmax .H. Write brief notes on the eect of pH. Write about various types of enzyme inhibition. enzyme concentration and presence of inhibitors on the activity of the enzymes. temperature. Bio chemistry (1995) W. K. 6. J (2000) Practical Biochemistry. 130 . Freeman.and Walker.

It is a reversible reaction that takes place in the presence of acid catalyst. Eventually it will attain equilibrium. 0(l) ∆GR = . k1 /k2 ) that can be independently calculated using the following relation: ln ∆HR K 1 1 = [ − ] K0 R T0 T 0(l) (38. Reaction CH3 COOH + C4 H9 OH ←→ C4 H9 COOCH3 + H2 O Acetic Acid + Butanol ←→ Butyl Acetate + Water Theory The synthesis of butyl acetate is done through esterication of acetic acid with n-butanol. The speed can be measured using a non-contact type tachometer. If the reaction is performed in a batch reactor.e. The catalyst used in the present experiment is a solid heterogeneous catalyst. The reaction is performed in a 300 ml glass reactors equipped with stirrer and condenser and placed in respective heating chambers for the attainment of the required temperature.8. reaction takes place on the surface of the catalyst. 131 .1) where K is the reaction equilibrium constant (i. enabling conducting ve runs at dierent temperatures simultaneously. The ester has wide application as a versatile solvent in chemical industry.38 Kinetics of a (Solid-Liquid) Esterication Reaction Aim To determine the reaction rate constants for the forward and backward reactions for esterication of acetic acid with butanol at dierent temperatures.3. K 0 = exp[− ∆GR ] RT0 0(l) Data: ∆HR = .887 kJ/mol. Digital temperature indicators are provided to measure the temperature of the reaction mixture in all the reactors. the conversion will increase and the reaction rate will drop with respect to time.2) where. The stirrer is driven by a motor with a control over the speed of agitation.889 kJ/mol 0(l) Apparatus The set-up consists of ve heating chambers whose temperature can be set independently thus. Hence. Kinetic Model Among all the models the simplest model is the pseudohomogeneous model given by the following rate equation: − rCH3 COOH = k1 CCH3 COOH CC4 H9 OH − k2 CC4 H9 COOCH3 CH2 O (38.

4. Place the reactors in the oil baths. Consider this time as the zero reaction time. Once the desired temperature of the reaction mixture is attained. 2.Procedure 1. 3. add the measured quantity of cation exchange resin (Amberlyst-15) in the reactor. Titrate weighed quantity of the sample against 0. Take measured quantities of acetic acid and n-butanol in the two reactors. Increase the speed of agitation to 1200 rpm. 6.5 M NaOH. Record the titration readings and calculate conversions at every time interval. Set the temperatures of the heating chambers (atleast four) at the desired levels and start heating. start slow stirring and observe the reactor temperature. Outline of the Process Data Mole ratio of reactants: Amount of catalyst: 132 . Keep removing the samples as per the time intervals indicated in the tables. Remove samples from all the reactors. 5.

1: Schematic diagram of the Esterication setup 133 .Figure 38.

Observation and Results Table Chamber 1 Temperature = ____ Chamber 2 Temperature = ____ Time Weight of Titer Val. Conversion Time Weight of Titer Val. Conversion Time Weight of Titer Val. Conversion (min) sample (g) (ml) (Xobserved ) (min) sample (g) (ml) (Xobserved ) 0 5 10 15 20 30 45 60 k1 k2 k0 for forward reaction 0 5 10 15 20 30 45 60 k1 k2 = k0 for backward reaction = E for forward reaction = E for backward reaction = 134 . Conversion (min) sample (g) (ml) (Xobserved ) (min) sample (g) (ml) (Xobserved ) 0 5 10 15 20 30 45 60 k1 k2 0 5 10 15 20 30 45 60 k1 k2 Chamber 3 Temperature = _____ Chamber 4 Temperature = _____ Time Weight of Titer Val.

The rate equation can be written as dX/dt = k1 × f2 (X) 2. The rate equation can be integrated to give k1 t = f1 (X) 2. 5. 2. 2. Evaluate Arrhenius parameters k0 and E for both backward and forward reactions from the graph. Calculate dX/dt at each time interval for X vs t plot. Calculate the conversion at all times for each temperature and plot the kinetic data (X vs t) for comparison. Find f1 (X) 3. Suggest the algorithm to evaluate k1 by regression analysis. Plot ln k1 and ln k2 vs 1/T . Find f2 (X) 3.Calculations 1. Calculate k1 and k2 from the above plot. how will you evaluate k1 and K from the kinetic data you have generated? 135 . where X is conversion. Plot dX/dt vs f2 (X). Conclusion and Comments Questions 1. 4. Plot f1 vs t to get k1 and k2 Dierential Analysis 1. Integral Analysis 1. 2. If K is not known. Calculate the reaction rate constant by Integration and Dierential method Integral Analysis 1.

3) Butyl acetate is an industrially important chemical and nds application as a useful solvent in many processes. Reactive distillation makes use of this concept and improves the yield of a reversible reaction. in the above system if one wants to remove D.1) (39.39 Batch Reactive Distillation Aim To examine the potential of batch reactive distillation in enhancing the reaction conversion. Denition of Batch Reactive Distillation Batch Reactive Distillation (BRD) is dened as a batch distillation system wherein reaction takes place in either reboiler or condenser or in the column or at more than one of these locations. For example. the reaction can be shifted in the forward direction and conversion of C can be enhanced. Reaction of Interest The reaction considered in the present experiment is esterication of acetic acid with butanol to give butyl acetate and water. Table 1 gives the boiling points of the components involved in the reacting system. CH3 COOH + C4 H9 OH ←→ C4H9COOCH3 + H2 O (39. The important limitation of reactive distillation is that the volatilities of the components involved should be favorable. Table 1: Boiling Points of Components Components Acetic Acid n-Butanol n-Butyl Acetate Water Boiling Points ◦ C 118 117.7 126. It has a potential to lower the capital and energy cost of the process. Theory Consider the following reversible reaction.2) The law of mass action for this reacting system is given by K= [C][D] [A][B] If C is the desired product Le Chatelier's principle says that if D can be removed simultaneously during the course of the reaction. it should either have the highest volatility or it should form a minimum boiling azeotrope with one or more than one component in the system.3 100 136 . A + B ←→ C + D (39.

Note down the temperatures. 3. 1.If we want to increase the conversion towards butyl acetate. The condenser (C2 ) serves as a reux condenser to reactor R2 . The reactors are R1 is connected to a distillation column (D) packed with ceramic raschig rings. ternary mixture water. butanol and butyl acetate). in reality. the liquid form two phases. then the azeotrope is called as heterogeneous azeotrope. The aqueous phase is almost pure water and can be removed easily. Increase the speed of agitation to the mark on the speed control device (it corresponds to 1000 rpm). Apparatus The set up consists of two identical reactors (R1 and R2 ) of about 1 lit capacity. The impellers are driven with the help of a common motor (M ). Remove samples from reactors R1 and R2 and perform the titration analysis 2. as water will possibly carry other components along with it in the overhead product. A Dean Stark type arrangement has been used to provide reux to the column. In the present case. Since this azeotrope has minimum boiling point. it does not happen. If on condensation of vapour. Start the water supply to the condensers and switch on the power supply to heating mantles for both reactors R1 and R2 and Put the stirrer on and start slow stirring and wait for the reaction mixture to boil. The column is insulated using asbestos ropes. Organic phase that consist of mainly butyl acetate and butanol can be recycled back to the column through reux.e. The boiling points in the table may indicate that water and other components have close boiling points and the ecient removal of water may not be possible. The speed is such that the resin particles suspend well in the reaction mixture and the mass transfer resistance across the solid liquid interface becomes negligible. A cock is proved to withdraw the water formed in the reaction. we have to remove water eciently during the course of reaction. ideally if one starts with stoichiometric mole ratio of butanol and acetic acid in the reactor. remove the sample (5 ml) from the bottom valves of both the reactors. baes and drain valve for sample removal. the azeotrope is heterogeneous and form two phases. at end of the run. instead of pure water one gets distillate composition close to the ternary azeotrope (i. Procedure The two reactors namely R1 and R2 are each charged with 440 gms acetic acid and 550 gms of n-butanol and 100 gms of strong cation exchange (acidic) resin as catalyst. Water forms ternary azeotrope with butanol and butyl acetate that boils at 87-90◦ C. Once the reaction mixture starts boiling. This conclusion is to be validated with the help of the present experiment. 4. Remove the samples from both reactors. the system should contain only butyl acetate in the reactor if losses of butanol and other components with overhead aqueous phase are negligible. 137 . The reactors are also equipped with temperature sensors. turbine type impellers. Both the reactors are externally heated with the help of a heating mantle. However. Hence. The overhead vapors are collected in the vertical condenser (C1 ). Nature of Azeotrope The azeotrope can be either homogeneous or heterogeneous.

The empty beaker (marked as "safety beaker") provided to you should be immediately placed below this valve and the instructor/demonstrator should be informed. Remove 2 ml sample in a conical ask by a pipette. 138 . Another indication for the saturation point is the constancy of reactor and top temperature with respect to time. Procedure for Sample Removal The sample from the reactor bottom may be collected by opening the drain valve. Keep removing samples from the reactors R1 and R2 after every 10/15 mins from the respective bottom valves and note down various temperatures (top and bottom for reactor R1 and only bottom for reactor R2 ). Make the correction for the hold up of water (5 ml) in Dean and Stark apparatus. The sample should be free from the resin particles. The condensate is collected in the Dean and Stark apparatus. Titrate with standard NaOH (0. 3. From the reactor R1 . Because of the voltage uctuations the speed of agitation may rise or fall suddenly. The analysis will give the indication of acid content in the mixture. The drain valves may leak during the course of the run. 2. You will observe that the condensate is a two phase mixture. This liquid is disposed to the waste bottle and again a fresh sample is taken by following the above procedure. Collect samples of aqueous layer after every 10/15 min. Start removing water so as to maintain its level at the mark shown on the arm of the Dean and Stark apparatus. When the acid content does not change with time. 8. Note the total amount of water removed (P). The initial quantity is rejected in order to purge the sampling line. 10. Some important practical problems During the experiment following things can go wrong.5. 2. Wait till the arm of this apparatus gets lled with liquid and the reux begins. Perform the analysis of all the samples by titration against standard NaOH.1 N) solution and phenolphthalein as indicator. The regulator position may be adjusted accordingly in such case. Outline of the Process Analysis by Titration 1. 9.5 ml of the sample is collected in the sample bottle and the valve is closed. 6. the saturation point is obtained. Remove samples of the organic layer after every 10/15 min. 7. Put the stirrer and heating mantle o. About 4. The students should take necessary action mentioned below or report to the instructor/demonstrator: 1. Dilute the sample with water (about 25 -30 ml). vapors move to the distillation column and eventually reach the condenser and get condensed. Stop the run at this stage.

Figure 39.1: Schematic diagram of Batch Reactive Distillation 139 .

3. OBSERVATIONS Titration reading of the reaction mixture: Readings when reaction mixtures from R1 and R2 start boiling: Time: R1: R2: Temperatures: R1 (Top): R1 (Bottom): R2: Titration reading: R1: R2: Observation Table Reactor R1 (batch reactive distillation) Sample Time(min) 1 2 3 4 5 Reactor R2 Temperature Titration Reading Cumulative Amount of Top Reactor Top (org) Top (aq) Reactor Water removed (P gms) 10 20 30 40 50 Sample Time (min) Temperature Titration Reading (mL) 1 2 3 4 5 10 20 30 40 50 Results 140 . Inform the instructor/demonstrator immediately. The stirrer of the reactor may stop suddenly.

e.Sample Time Titration Reading Acidity of Sample Conversion (%) Conversion (%) based (min) (mL) V1 (A) (V1 × 0. reaction followed by distillation)? Why? 7. Plot proles of temperature. 4. Is batch reactive distillation an economically attractive option to the conventional approach (i. What if the azeotrope is not heterogeneous? 5. Why the reaction temperature changes with time? 3.1)/2. How much acetic acid is lost through distillate? Does that make a signicant impact on the conversions calculated? 141 .0 (A0 − A)/A0 on water removed Enhancement obtained in batch reactive distillation system = Conversion in reactor R1 − Conversion in reactor R2 Conversion in reactor R2 Conclusions and Comments Questions 1. What is Le-Chatelier's principle and how it is applied in the present experiment? 2. What is the eect of speed of agitation and particle size in this experiment? 6. What is azeotrope? Explain its relevance in the present experiment. rate of water removal (only for R1 ) and conversion with respect to reaction time for both R1 and R2 . 8.

All these properties make micelles to catalyze a reaction. Chemicals Diethyl aniline (DEA). The counter ions located in the double layer can exchange ions with the bulk. However. Hydrophobic groups of surfactant molecules form the core of micelles while the hydrophilic head groups are located at the interface with water and the relatively small counter ions of the ionic micelle are located in stern layer.40 Micellar Catalysis Aim Study of instantaneous reaction by micellar catalysis. cetyl trimethyl ammonium bromide (CTAB) Reaction Figure 40. stirrer with motor assembly. The reaction can be studied using dierent surfactant. Micelles can solubilize the sparingly soluble organic reactant. surfactant molecules form micelles. syringe. micelles provide high interfacial area. HCl. The size of the micelles is comparable to the molecular size. Apparatus Reaction kettle. pipette. Typically micelles have average radii of 12-30 Å. standard asks.1: Conversion of Diethyl Aniline to Diethylaniline hydrochloride Theory When the concentration of a surfactant in a solution exceeds certain limit known as critical micelle concentration (CC). due to small size. 142 . cetyl trimethyl ammonium bromide at concentration above CC. Most of the counter ions are however located in the electrical double layer where they are completely dissociated to form charged aggregates and are able to exchange with ions in the bulk of the solution. Due to this small size. anionic as well as cationic and enhancement factor can be found. thistle funnel. number density of micelles is quite high. The above reaction is studied in presence of cationic surfactant certied (CTAB). etc.

Rate Equation R = kL [DEA∗ ](1 + q) Where. The enhancement factor φ is dened as: φ= slope in presence of surfactant slope in absence of surfactant Procedure 1. −V d[HCl] =R×A dt (40. The reaction is monitored for 30 min. The above procedure is repeated in presence of CTAB to observe the eect of micelles. 6. Slowly add 85 ml of DEA by means of a funnel so that it spreads on the surface of water. In a model stirred cell reactor. Position the impeller in the aqueous phase and set at a speed of 45-50 RPM so as to maintain a at interface. mol m−2 ms−1 . V is volume of aqueous phase.6) line with Slope = Therefore. 143 . (40. and diluted 300 times before analysis. 3. Add concentrated HCl through the thistle funnel into the aqueous phase to obtain a strength of 0. R = kL [DEA∗ ]q Therefore. 7. 4. This is zero reaction time. 1 + q ∼ q = Hence. From the above equations −V d[HCl] DDEA 1/2 = kL [HCl] A dt DHCl (40. q= [HCl] DDEA 1/2 [DEA∗ ] DHCl (40. 5. R = kL [HCl] DDEA 1/2 DHCl (40. plot of ln [HCl]i /HCl vs t will give a straight (kL A/V )(DDEA /DHCl )1/2 . Aqueous phase sample (1 ml) is withdrawn by means of a syringe at a time interval of every 3 min. add 250 ml of water.2) Where. DDEA and DHCl are diusivity of DEA and HCl respectively in the aqueous phase. If q is large. 2. ln [HCl]i kL A DDEA 1/2 = t HCl V DHCl (40.3) Material balance for HCl in the aqueous phase yields. R = specic rate of extract of DEA into HCl. kL = mass transfer coecient. The solution of the above equation is therefore.1) s−1 .5) The initial condition is [HCl] = [HCl]i at t = 0. [DEA∗ ] = solubility of DEA in aqueous phase.4) where.1 N. mol m−3 .

Calibration A standard plot is made of DEA-HCl of the following concentration: 1. 3 × 10−3 M 3. 10 Observation Table II (with CTAB) S. 5 × 10−3 M Observations HCl = DEA∗ = mol m−3 mol m−3 Observation Table I (without CTAB) S. 2 × 10−3 M 2. All the aqueous phase samples are therefore analyzed on UV-VIS spectrophotometer at the wavelength of 253 nm.N. Time (min) Concentration 1 2 .N.Analysis The salt DEA-HCl formed in the aqueous phase shows an absorbance maxima at wavelength of 253 nm. 4 × 10−3 M 4. 10 144 . Time (min) Concentration 1 2 .

Calculate q [HCl] q= DEA∗ DDEA DHCl 1 2 2. kL (without CTAB) = mol s−1 5.Results 1. Slope in presence of CTAB = 4. Slope in absence of CTAB = 3.N Time (min) Concentration (without CTAB) Concentration (with CTAB) 1 2 . 10 φ Conclusions and Comments 145 . kL (with CTAB) = mol s−1 Result Table S.

[C9 H7 N ] is concentration of quinoline in the organic phase. it separates out from the reaction mixture. k2 is the reaction rate constant. Therefore. mol m−3 . Vorg is the volume of organic phase. It can be represented as follows: R3 N + R X −→ R3 N + R X − (41. Vaq is the volume of aqueous phase. a plot of [Br− ] vs time is a straight line. Appreciable conversion can be obtained by mixing suitable amount of quinoline and 1-bromobutane in a reaction vessel and shaking for two hours. mol m−3 . [Br− ] is the concentration of bromide ions in the aqueous phase. the concentration of both n-BuBr and quinoline can be assumed as constant. Since quaternary salt is insoluble in the organic phase. stoichiometric amounts of amine with the appropriate alkyl bromide/iodide. m3 mol−1 s−1 . The rate expression can therefore be written as: Vaq d [Br− ] = k2 [n-BuBr][C9 H7 N ]Vorg dt (41. cm3 . This diculty is solved by adding the second phase viz. Reaction is rst order with respect to quinoline and 1-bromobutane.1) These reactions are usually conducted by warming for a few hours.2) Where. A typical example of this. 146 . [n-BuBr] is the concentration of 1-bromobutane in organic phase. cm3 . is alkylation of quinoline with 1-bromobutane. This reaction can be carried out at 80◦ C. Aqueous phase can be sampled for Br− analysis. The slope for this line is: S = k2 [n-BuBr]i [C9 H7 N ]i (Vorg /Vaq ) where [n-BuBr]i and [C9 H7 N ]i represent the initial concentration of 1-bromobutane and quinoline respectively. water which extracts quaternary salt from the organic phase. mol m−3 s−1 . The rate constant k2 can be estimated from the slope. Formation of solid makes it dicult to accurately sample the reaction mass from analysis. Since conversion of n-BuBr during the experiment is small (< 10%). Reaction Theory The most common and useful method for preparation of quaternary ammonium salts is by alkylation of tertiary amines with an alkyl halide.41 Homogeneous Reactions Aim To study kinetics of homogeneous reaction of quinoline (Q) with 1-bromobutane (BuBr).

5. Observation Table S. 50 ml of 1-bromobutane and 100 ml of water in a reactor. This corresponds to zero hour sample. after allowing the two phases to separate. Analysis Selective ion electrode is provided along with the reference electrode and the Br− electrode. Aqueous phase sample (1 ml) which is withdrawn at every 20 min interval is quenched with a drop of concentrated HNO3 and then diluted to 100 ml in a standard volumetric ask. Add 1 ml ionic adjuster (ISA) to this solution and read concentration in ppm on the meter. silver ions dissolve from the membrane surface and electrode develops a potential due to the silver ion concentration. set in water bath maintained at 80◦ C.N. Take 50 ml of Quinoline. 6.3) Conclusions and Comments 147 . Continue the reaction for 2 hours.Procedure 1. 3. When the membrane is in contact with a halide solution. determined by the sample halide ion concentration. 4. 50 ml of this is taken for analysis. Time (min) Concentration (ppm) Calculations k2 = slope × Vaq [n-BuBr]i [C9 H7 N ]i Vorg (41. The meter is calibrated with standard bromide solution. Withdraw sample from the aqueous phase. 2. by analyzing for Br− in the aqueous phase using a specic ion electrode meter. Take samples from the aqueous phase at an interval of 20 min. This concentration is in turn. The halide electrode consists of silver halide/silver sulde membranes bonded into the tip of an epoxy electrode body. The reaction is monitored. Stir the reaction mixture at 200-250 rpm so as to form a completely dispersed system.

Nitrating mixture. Equipment Reaction Kettle. ρ = 1. Spectrophotometer. Rate = k2 [RN O2 ][N O2 ]+ = k2 [RN O2 ][HN O3 ] (42. nitrobenzene in presence of the nitrating mixture.e. Geared motor.e.735 g/ml. HN O3 + 2H2 SO4 N O2 H SO (+) + H3 O(+) + 2H2 SO4 (−) (−) i.42 Interfacial (Liquid-Liquid) Nitration Aim To study the kinetics of nitration of nitrobenzene (NB) in a stirred cell reactor at a liquid-liquid interface. Thistle funnel. 2. and K is the extent of dissociation of HNO3 to yield NO(+) ion. HO − N O2 − 2− → HSO4 − −4 H SO + HO(+) H (−) N O2 − 2− → H3 O(+) + HSO4 − −4 + N O2 (−) (+) The controlling step is the attack of N O2 on nitrobenzene.).1: Nitrobenzene to Di-nitrobenzene Reactants 1. Standard ask. Nitrobenzene (A. Reaction Figure 42. 148 . Impeller. NaOH solution.2 g/ml. The reaction 2 exhibits second order kinetics. Theory The reaction involves electrophilic substitution of substrate i.R. Syringe.1) where k2 = Kk2 . ρ = 1.

[NO2 ]∗ = concentration of nitrobenzene and nitronium ion per unit area of monolayer. and k2 = interfacial reaction rate constant. the reaction can occur in the interfacial mono-layer in addition to the reaction in the bulk. The sample is quenched with distilled water and the organic phase after separation is analyzed for m-DNB content by Janovsky test. The reaction is conducted at at inter- 6. 4 NO(+) and NO(−) and organic phase containing polar aromatic molecules. Therefore.0 ml) from the organic phase at an interval of every 15 min for 1. mol/h. The eect of the degree of agitation on the overall rate can therefore be studied in order to check whether one or the other mechanisms are dominant. Exactly opposite behaviour is exhibited by the interfacial reaction. With the help of thistle funnel. 149 . Start the motor and set the impeller speed. mol/m2 . Set the impeller at the interface. mol/h. and Ri and Rb = rate of reaction at interface and bulk respectively. 3.3) where. m2 /mol h. face/dispersed system. Charge 100 ml of nitrating mixture to the Stirred Cell reactor.2) where R = total rate of reaction. the overall rate of reaction may be written as: R = Ri + Rb (42. and A = interfacial area.Industrial nitration involves two phase system. HSO(−) . This sample corresponds to zero reaction time.5-1. Procedure 1. The reaction is monitored for the presence of m-dinitrobenzene (m-DNB) by withdrawing samples (0. Thus. 5. slowly add nitrobenzene (100 ml) so that it is evenly spread on the surface of the nitrating mixture. The charged species 2 3 present in the bulk aqueous phase will tend to concentrate at the interface depending on the surface charge. The rate of bulk reaction depends upon volume of the aqueous phase while it is independent of the interfacial area. Ri and Rb can be expressed as: Ri = k2 [RN O2 ]∗ [N O2 ]∗ A Rb = k2 [RN O2 ][HN O3 ]V (42. 4.5 hrs. aqueous phase containing ions such as H(+) . Withdraw sample (1 ml) from the organic phase. [RNO2 ]∗ . 2. m2 .

Concentration of m-DNB per weight of sample = x × 10−6 weight of sample per ml of acetone 2.). The sample is analyzed after 10 min on a UV-spectrometer. 10 ml of this sample is taken in a beaker to which is added 0. Note the absorbance at 573 nm wavelength (λ).01719 where. x = concentration of m-DNB in acetone (mg/l) 1. of sample taken Absorbance Concentration of DNB for analysis per weight of sample Conclusions and Comments 150 . Slope obtained from the plot corresponds to the rate of reaction. Draw a graph of % conversion vs time.6 ml of NaOH solution (0.1 g) is taken in a volumetric ask (25 ml) and diluted with acetone.25% by wt. of sample × total weight of organic phase moles of HNO3 in nitrating mixture Determine % conversion for each sample. Observations and Results Time (min) Wt.Analysis The organic phase sample ( 0.123x + 0. % conversion based on HNO3 taken moles of DNB formed 100 × wt. Violet colour starts developing. Calculations Equation of the calibrating curve y = 0.

then the k th value is left unchanged (rounding down). The main problem associated with regression analysis is the lack of thought which goes into verifying whether a linear model is appropriate.e..001360 all have 4 signicant digits. • Fixed-point: xed number of decimal places: 1. Truncation and Round-o errors Obviously. and (2) lack of understanding of the use of regression analysis. Double precision uses −308 < e < 308 (−1020 < exp2 < 1020). A signicant aspect of data representation is the concept of signicant digits.1234 × 105 or 0. ¯ For single precision calculations. there could be loss of signicance in the storage of numbers at lower precision. there is a loss of signicant digits. Decimal places are discarded by chopping them o (truncation) or by rounding them o. then add 1 to the k th • If the number discarded is half the unit in the k th place (i. • If the number discarded is more than half the unit in the k th place. lack of knowledge of the least count associated with devices/measurements. t is usually 8 and |e| < M (M is the largest exponent that is allowed). Usually m is limited to 8 digits and hence a is now stored as a = ±m. even decimal. and analyze your data accordingly. Any number a may be represented as ±m. and lack of understanding of how errors propagate during successive calculations..1386 × 10−6 etc.10e where ¯ ¯ m = 0. −38 < e < 38 (−125 < exp2 < 125) where exp2 is the exponent in base 2 (M =38).1234E05. Number representation Data may be represented by xed-point or oating-point representations. • If the number discarded is less than half the unit in the k th place.360 is dierent from 1.A Data Analysis There are two common mistakes associated with most computations as observed in student reports: (1) lack of signicance in computed answers.10e where m is the mantissa (0. round o to the nearest 151 . The lack of signicance in most computations is the result of three causes: unnecessary use of all reported digits as displayed by calculators/computers.1 ≤ m < 1) and e is an integer.36. It is important to appreciate that 1. because we cannot represent innity on a computer).000. In both cases. Rounding o involves discarding digits from (k + 1)th place onwards. this last digit of signicance is a function of the least count of the measuring device. 1. 0. The numbers 1360.dt and d1 > 0. It is expected that you familiarize yourself with the discussion below. −0.128 • Floating point: 0.360. value (rounding up).d1 d2 . Numbers smaller than 10−38 would give underow errors (which are handled by treating the value as 0) and values larger than 1038 cause overow errors (problematic.836. In the context of measured values. 36823. 12. = 5).

the relative truncation error is ¯ ¯ m−m ¯ a−a ¯ ∼ ≤ 101−t a m The absolute error when the true value a is measured as a is = a − a. and that |m| ≥ 0.3.4 and 3. The relative error of a is r = (a−˜)/a = /a. Error propagation Let x = x + ˜ Addition: 1 and y = y + ˜ 2 where | 1 | ≤ β1 and | 2 | ≤ β2 1 | | = |x + y − (˜ + y )| = |(x − x) + (y − y )| = | x ˜ ˜ ˜ + 2| ≤ β1 + β2 Subtraction: | | = |x − y − (˜ − y )| = |(x − x) − (y − y )| = | x ˜ ˜ ˜ 1 − 2| ≤ β1 + β2 For both addition and subtraction.6.Therefore 3.10e is approximated by a = ±m. 2 and 1 places gives 1.10e . Rounding o 1. the error of the result is the sum of absolute errors..3. Example: a = 10.45 and 3. 1. and hence x/y − x/˜ ˜ y x/y ≈ 1 x − 2 y ≤| r. Division: The real ratio may be written as x y = x+ ˜ y+ ˜ 1 2 = x+ 1 ˜ x+ ˜ = y (1 + 2 /˜) ˜ y y ˜ 1 1− 2 y ˜ + 2 2 y2 ˜ − ..2 and a ˜ ˜ ˜ = 10.10e . While errors in the representation of individual numbers may look small.2! When a = ±m. But a is usually unknown.1 + βr. 152 .25 and 1. and so this is approximated ˜ a with r = (a − a)/˜ = /˜.1 | +| r.10e is approximated by a = ±m. Usually is unknown.1) |m − m| ≤ 10 ¯ m−m ¯ 101−t a−a ¯ ∼ ≤ a m 2 Chopping o is obviously simpler.2 | ≤ βr.1 | + | r.1 + βr.5 gives = −0.254. When a = ±m.25 to one place gives 1.2 2) = 1y + 2x − 1 2 xy ≈ 1y + 2x 1 2 ≤ + xy x y where we have assumed | 1 2 | | 1 | and | 2 |. the relative rounding o error is (noting that ¯ ¯ −t /2.2 | ≤ βr. and so we use bounds such as β where | | ≤ β and ˜ a a | r | ≤ βr . Note that rounding o 1. ≈ x ˜ ˜ 1 2x + − y ˜ y ˜ y y ˜ ˜ where 1 2 and higher terms are neglected.2535 to 3.55 when rounded o to one decimal place become 3. but errors would be larger. the relative error of the result is the sum of relative errors.2 For both multiplication and division. successive manipulation of such numbers would cause the total error to blow up. Multiplication: The relative error r of xy is ˜˜ | r| = xy − xy ˜˜ xy − (x − 1 )(y − = xy xy ≈ | r.

153 ..37 6.95 which gives x1 = 39.6) 0. • Method 1: For ax2 + bx + c = 0.3 ) = (x(1 + r. (0.7-35. digits 5 4 3 2 1 a/(b − c) a(b + c)/(b2 − c2 ) 0. Then the ˜ ˜ ˜ oating point representation of their sum would itself be stored as a oating point value (˜ + y ). then (˜ + y ) = (˜ + y )(1 + x ˜˜ x ˜ r.794 8.60) signif.0004 = 1.0004) + 0.1426 = 0. Calculation 0.0004) + 1.0004 + 0.001 but (1. 0.724-35.0 = 20.13 × 10−2 with the loss of two signicant digits.81534/(35.4 6 Example: Quadratic roots: Find roots of x2 − 40x + 2 = 0 to 4 signicant digits.000 = 1.1 + y(1 + r. √ √ −b + b2 − 4ac −b − b2 − 4ac .8153/(35.2 ))(1 r.3698 6.2 ) r.00 ± 398.815/(35.Loss of accuracy The causes of loss of accuracy usually are Floating point errors and Experimental errors.370 6. the mean is computed by summing all the numbers using a loop. It may be more reliable to sort the numbers and to then add them up.1 ) r. This can be an issue for example. for better accuracy.000. x2 = x1 = 2a 2a √ gives x = 20.2 ) r.00 ± 19.82/(36-36) 6.05.1439 − 0. Creeping roundo/truncation: Using the denition of relative errors.000 + 0. Example: Computing the ratio a/(b − c) can be problematic if b and c are of almost equal value.1 + r. x = x(1 + r.3698437. 4. Magnication: Errors get magnied usually on multiplication/division as explained before.3698 6.2 ) where x and y are the oating point representations of x and y .95 and x2 = 0. Loss of signicant digits by subtraction cancellation Example: Subtraction cancellation of two numbers of ∼same size: 0.15 division by 0 - 6. x ˜˜ If the relative error in this representation itself is r..3 ) r. Negligible addition: adding a small number to a larger one with roundo could result in the smaller number being drowned out.1 ) and ˜ y = y (1 + r.3 . Add the smallest numbers rst.596)=6. and then dividing by n.0013 = 0. To 4 signicant places (4S). 3.3 = (x + y) + (x + y) + (x +y + (x +y 2.72 − 35. when computing the mean: for n values.3 r. Floating point errors These are usually of 4 types: 1.

• Method 3: Use b1 = −b . Lxx .05006. (α and β are population parameters. 2a c1 = c . Regression analysis Given a model where we believe that y = α + βx. • Store intermediate values in extended precision. First note that the values a and b represent the best possible estimates of α and β given available experimental measurements (xi . yi ) = (xi .. 1 r1 = |b1 | + √ d If b1 < 0. What roots does this method give? Other tips • Use fewer operations to reduce error: For example. The deviations of the actual experimental points ˆ from the line are yi − yi = di = yi − a − bxi .95 and x2 = 2. use r2 = c1 /x1 . and a and b represent sample estimates of those parameters). Lxy = i=1 (xi − x)(yi − y) = i=1 xi yi − nx y 154 . a = y − bx n i=1 yi where x= n n n i=1 xi n 2 y= n n n Lxx = i=1 (xi − x) = i=1 2 x2 i − n(x) . This gives x1 = 39. For y = a0 xn + a1 xn−1 + . y=y*x+a_{i}. Instead use the identity 1 + cos(x) = 2(sin(x/2))2 .95 = 0. yi ). 2a x2 = c ax1 using the observation that x1 + x2 = −b/a and x1 x2 = c/a. use x1 = −r1 and if r1 = 0. end This results in 2n operations only. The best t line tries to minimize S = sum of squared ˆ distances of points from the line (hence called the method of least squares) n n S= i=1 d2 = i i=1 (yi − a − bxi )2 It can be shown that the best estimates of β and α are b= Lxy . Instead of computing x4 as x × x × x × x. with one addition and one multiplication per iteration. use nested multiplication if possible. use a loop: y=0. For i=1 to n+1. • Find alternate series forms.000/39. a d = b2 − c1 . use u = x × x and then use x4 = u × u. + an x + an+1 .• Method 2: x1 = −b + √ b2 − 4ac .. For example 1 + cos(x) is dicult to measure at x ≈ π since cos(π) = −1 (subtractive cancellation). We need a line such that (xi . we wish to estimate the `best-t' regression line y = a + bx. a + bxi ).

or if the variables are themselves swapped (x is called y and vice-versa). for the parameters involved. r = Lxy / Lxx Lyy where Lyy is = n (yi − y)2 = n yi − n(y)2 . the standard deviation associated with these measurements. Clearly. Note that r is unchanged if the units of x and y are changed. Notes • The least-squares linear regression method assumes that the data ts a linear model. These standard deviations are representations of the errors that we have already discussed. but propagation of standard deviations are ignored. However while small values of x (and therefore small errors in the measurement of x) may not signicantly inuence the shape of the hyperbolic curve (and estimation of parameters from that curve). 155 . • A necessary aspect of accurate parameter estimation is identication of condence intervals • A typical trick used in parameter evaluation of a nonlinear model is to rst convert it to a linear form and then apply linear regression. blind application of this statistical approach can be dangerous. For example. b however would be aected by swapping of variables or a change in units. It is common to perform replicates to identify an average value. Nonlinear regression approaches exist. It is also important to compute from these replicates. Belief in the estimates is increased on increasing the sample size (To increase your belief that a coin is fair. y = ax/(b + x) may be inverted to yield the linear relationship 1/y = (1/a) + (b/a)(1/x). The propagation of errors reects the situation that typically arises when the mean values of various variables are manipulated using various arithmetic operations. r ranges from -1 i=1 i=1 to +1. and r = 0 indicates that x and y are not correlated. toss it more times). r is related to the slope of the best-t line b.The sample correlation coecient is a measure of association between the two continuous variables 2 x and y . It is possible (and common) to get excellent regression values (close to 1). yet the data might instead be better described by a higher polynomial. they have a huge impact on the calculation of the slope and intercept of the inverted (linear) form. r indicates a linear relationship between the variables. but clearly even then. whereas b describes the precise linear relationship between them.

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